CN102899087A - 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 a kind of middle coalite tar deep processing technology method.
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 minimum coal of degree of coalification.The characteristics of brown coal are that moisture is high, proportion is little, volatile matter is high, non-caked, chemical reactivity strong, poor heat stability, thermal value are low, contains the humic acid of different quantities.The raw material that is used as fuel, gasification also can be used to extract montanin wax, humic acid more, makes sulphonated coal or gac etc.The volatile content of long-flame coal is also very high, does not have or only have very little cohesiveness, and easy firing has very long flame during burning, so the 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.The bottle coal volatile matter is high, and gelatinous layer is thicker, poor heat stability.Separately coking of long-flame coal, but the coke of producing is elongated frangible, and shrinking percentage is large, and longitudinal crack is many, and is anti-crushing relatively poor with wear resistance, so can only be used as coal-blending coking, also can be used to make coal gas, produces 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 half afocal is produced in decapacitation when middle low-temperature pyrolysis, 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 gasifies and makes 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%.Because coal directly burning can cause more serious dust pollution, and is therefore more and more higher as the ratio of domestic fuel take coal as the raw material production town gas, the middle coalite tar amount of simultaneously association also increases greatly.Because semicoke is the main raw material of producing ferrosilicon and calcium carbide etc., the device of therefore producing low-temperature pyrolysis in the coal of semicoke also is more and more, and the middle coalite tar amount of simultaneously association is also increasing greatly.At present, the treatment process of the factory of above-mentioned middle low-temperature pyrolysis production semicoke and the middle coalite tar of gasification factory by-product is directly burnt as low-quality fuel oil behind acid-alkali refining, or directly burns as emulsion fuel after the emulsification.But wherein the impurity such as institute's sulfur-bearing, nitrogen become SOx and NOx and discharge into the atmosphere and cause topsoil in combustion processes, and produce again large amount of sewage in the acid-alkali refining process.
Because middle coalite tar comes from the dry distillation of coal and gasification, is the thermally splitting product, so the composition of middle coalite tar is very complicated.The chemical constitution of middle coalite tar mainly is aromatics and alkene, and Determination of Alkane Content is less, also contains and contains on a small quantity oxygen, nitrogenous, sulfocompound.Oxygenatedchemicals mainly is to have weakly acidic various phenols, and nitrogenous compound mainly is to have weakly alkaline pyridine, quinoline and their derivative, and sulfocompound mainly is thiophene, mercaptan, thiophenol, thioether etc.Deficiency along with the China's oil resource, the year by year increase of crude oil import ratio take middle coalite tar as stock oil, is adopted more suitable complete processing production clean fuel or the petroleum products suitable with petroleum products, not only have significant economic benefit, also have obvious social benefit simultaneously.
The deep processing method of middle coalite tar once received much attention and dropped into substantial contribution and manpower studies in twentieth century 50, the sixties.But find and exploited oil that along with grand celebration, Xinjiang and other places oil is produced vehicle fuel as the very fast coal tar that replaced of main energy sources.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, since the growing tension of petroleum resources, the increasingly stringent of environmental regulation, and the deep processing of coal tar begins to come into one's own again.Chinese patent CN1205302C has proposed a kind of complete processing of middle coalite tar: middle coalite tar at first carries out delayed coking, produce coke and coking distillate, coking distillate enters extraction tower afterwards, in extraction tower, add alkaline solution, extract phenols, the fraction oil of dephenolize enters separation column, fractionates out the cuts such as petroleum naphtha and diesel oil again.But this technique patent has following shortcoming and defect:
1, dephenolize is put into phenols can corrode delayed coking unit after the delayed coking, affects service life of equipment.
2, delayed coking scheme can reduce target product liquid to be received, and reduces economic benefit.Although and delayed coking can remove the impurity such as sulphur in the part coal tar, nitrogen, very major part still is retained in the coking distillate, can not be removed in a large number, still can cause environmental pollution when burning.The more important thing is that the distillate after the coking contains more alkene and colloid, can affect the hot stable qualitative of oil product, cause the engine infringement.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of middle coalite tar complete processing, remedy the deficiency of above-mentioned prior art processes, not only can production high-quality oil product, and coalite tar in farthest utilizing.
The coalite tar deep processing method comprises following processing step among the present invention:
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 obtains of step 1 carries out phenol removal, obtains phenol products and dephenolize oil;
3, the heavy oil that obtains in the 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 coking naphtha, coker gas oil and the wax tailings that obtain of step 3 mixes with the dephenolize oil that lighting end, last running and step 2 that step 1 obtains obtain, carry out hydrofining and hydrocracking reaction, reaction obtains 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 the step 1, middle coalite tar carries out carrying out pre-treatment before the fractionation, pre-treatment mainly removes moisture and mechanical impurity, specifically can adopt the methods such as centrifuging, electrodesalting and electrodehydrating to carry out pre-treatment.Fractionation adopts the vacuum fractionation tower to get final product, cat head fractionates out lighting end, side line fractionates out carbolic oil and last running, obtain heavy oil at the bottom of the tower, the final boiling point of lighting end is generally and is not more than 180 ℃, the final boiling point of carbolic oil is generally and is not more than 240 ℃, and the final boiling point of last running is generally and is not more than 350 ℃, and the initial boiling point of heavy oil is generally and is not less than 340 ℃.
The inventive method, the described phenol removal of step 2 adopts the soda acid method for extracting, and the concrete operations mode is well known to those skilled in the art.Specifically can adopt conventional coal tar carbolic oil refining plant, the phenol cut that contains that the vacuum fractionation tower is told enters extraction tower, adds alkaline solution in extraction tower, and the phenates that extracts is through steaming stripping oil, sulfuric acid or CO
2Obtain phenol products after decomposing, obtain dephenolize oil after extracting phenol products.The phenol products that obtains generally comprises phenol, industrial cresols, ortho-cresol and xylenol etc.Also may contain the 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, delayed coking is preferably adopted in pyrogenic reaction described in the step 3, method well known to those skilled in the art is adopted in coking, but the delayed coking charging in this invention is the mixing oil of the hydrocracking section product unreacted tail oil in heavy oil (initial boiling point generally is not less than 340 ℃) and this invention at the bottom of the tower in the step 1.In addition, can add other suitable raw material, the sump oil that reclaims such as various poor residuums, catalytically cracked oil, field of Environment Protection etc.A kind of typical pyrogenic reaction operational condition is as follows: 400 ℃～550 ℃ of temperature of reaction, reaction pressure 0.15MPa～0.5MPa; 400 ℃～535 ℃ of preferable reaction temperature, preferred reaction pressure 0.17MPa～0.35MPa.
In the inventive method, hydrofining in the step 4 and hydrocracking can be adopted technological process well known to those skilled in the art, the hydrofining effluent generally need carry out separating treatment, the moisture that the impurity that removes in the hydrofining reaction process is particularly produced is from out, then carry out hydrocracking reaction, avoid hydrocracking is had a negative impact.A kind of typical method is to adopt two-stage hydrocracking technique, and the hydrofining reaction product at first entered separation column before entering hydrocracking reactor.Separation column is conventional atmospheric distillation plant, but with the hydrofining full distillate oil by fractionation after output gasoline fraction, diesel oil distillate and wax oil cut, gasoline fraction and diesel oil distillate directly go out device, the wax oil cut then carries out hydrocracking reaction, further carry out hydrocracking and produce gasoline fraction, diesel oil distillate and unconverted tail oil, gasoline fraction and diesel oil distillate directly go out device, and heavy oil (initial boiling point generally is not less than 340 ℃) mixes the charging as delayed coking at the bottom of the tower in unconverted tail oil and the step 1.If there is the raw material in other source, can be as required and above-mentioned unifining process and hydrocracking process co-treatment.
In the inventive method, the hydrofining in the step 4 and hydrocracking can be adopted catalyzer well known to those skilled in the art and processing condition.The hydrofining reaction condition is generally: volume space velocity 0.15～1.5h when 180～427 ℃ of temperature of reaction, pressure 10.0～17.0MPa, hydrogen to oil volume ratio 500: 1～3500: 1 and liquid
-1The most preferred reaction conditions of hydrofining reaction is as follows: volume space velocity 0.2～1.2h when 180～420 ℃ of temperature of reaction, pressure 10.0～16.0MPa, hydrogen to oil volume ratio 800: 1～3000: 1 and liquid
-1The hydrocracking reaction condition is generally: volume space velocity 0.15～1.5h when 360～427 ℃ of temperature of reaction, pressure 10.0～17.0MPa, hydrogen to oil volume ratio 500: 1～2000: 1 and liquid
-1The most preferred reaction conditions of hydrocracking is as follows: volume space velocity 0.2～1.2h when 380～420 ℃ of temperature of reaction, pressure 10.0～16.0MPa, hydrogen to oil volume ratio 800: 1～1500: 1 and liquid
-1
In the inventive method, the hydrogen that hydrofining and hydrocracking process need in the step 4 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 the hydrogen from methyl alcohol, the concentrate of low-concentration hydrogen can adopt this area ordinary method, such as pressure-changed adsorption concentrating method etc.
Gasoline fraction and diesel oil distillate that the inventive method obtains clean, and also are stable performances.In addition, utilize the singularity of coal tar component also to produce the high value added products such as phenol, industrial cresols, ortho-cresol, xylenol, liquefied gas and refinery coke.Really realized effective utilization of middle coalite tar, the work-ing life of more greatly having improved appliance arrangement.
Specifically, the inventive method also has following attendant advantages:
1, phenols has the deep-etching effect to equipment, and has high added value, therefore isolates first phenol products before to coal tar deep processing, has not only increased economic benefit, has prolonged simultaneously the work-ing life of coal tar deep processing appliance arrangement.
2, because coal tar contains the material of more solid dust and easy coking, above-mentioned substance is difficult for adopting other technologies to be isolated out, adopt delay coking process the material of solid dust and easily coking can be solidificated in the coke, 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, and the coke that therefore produces with coal tar is that low-sulfur is burnt, has been widely used.
3, the distillate after the delayed coking is passed through hydrotreatment again, can greatly improve the character of oil product, maximum ground produces high-quality petrol and diesel oil cut, is becoming tight in oil supply day, in the situation that the light-end products demand goes up, provide the source of supply of new light-end products.
4, coal gas adopts pressure-variable adsorption (PSA) technology the hydrogenation process of hydrogen proposition for destructive distillation coal tar through after purifying, and belongs to Matter Transfer and uses, without exhaust emission.After the more important thing is that the impurity such as sulphur in the raw coal, nitrogen enter in dry distillation gas and the destructive distillation coal tar by destructive distillation, can be sulphur and ammoniacal liquor with sulphur, azepine cycling of elements at an easy rate, namely increase economic benefit, reduced again the environmental pollution that burning dry distillation gas and coal tar are produced the petrol and diesel oil cut.
Description of drawings
Fig. 1 is the process flow diagram of coalite tar processing among the present invention.
Embodiment
The below is for a more detailed description to the present invention for example by technical process shown in Figure 1.
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 sees Table 1, send to and enter vacuum fractionation tower 1 after pretreatment unit removes mechanical impurity and water, 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 and the unconverted tail oil of hydrocracking section are mixed into delayed coking unit 3 and carry out heat scission reaction and produce the coking dry gas at the bottom of the tower, liquefied gas, coking naphtha, coker gas oil, wax tailings and petroleum coke, temperature of reaction is 465 ℃, reaction pressure 0.23MPa.Coking naphtha wherein, coker gas oil, the benzoline of wax tailings and separation column 1, enter hydro-refining unit 4 after carbolic oil extraction plant 2 isolated dephenolize oil 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, the hydrocracking reaction product separation is dry gas, liquefied gas, hydrotreated naphtha, hydrogenated diesel oil and unconverted tail oil, hydrorefined average reaction temperature are 320 ℃, pressure 15.0MPa, volume space velocity 0.5h when hydrogen to oil volume ratio 1000: 1 and liquid
-1Volume space velocity 0.3h when 380 ℃ of the temperature of reaction of hydrocracking, pressure 15.0MPa, hydrogen to oil volume ratio 800: 1 and liquid
-1Hydrobon catalyst is with alumina supporter, and the molybdenum oxide weight content is 15%, and the Tungsten oxide 99.999 weight content is 12%, and the nickel oxide weight content is 5%, and specific surface area is 185m
2/ g, pore volume are 0.35ml/g.(the silica/alumina molecular ratio is as 12 take 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 the cracking component, the Y zeolite weight content is 15%, the amorphous aluminum silicide weight content is 35%, and the Tungsten oxide 99.999 weight content is 28%, and the nickel oxide weight content is 8%, surplus is aluminum oxide, and specific surface area is 270m
2/ g, pore volume are 0.42ml/g.Hydrobon catalyst and hydrocracking catalyst carry out conventional prevulcanized before use to be processed.
Embodiment 2
The low-temperature pyrolysis coal tar of Shenmu County's brown coal, character sees Table 1, send to and enter vacuum fractionation tower 1 after pretreatment unit removes mechanical impurity and water, 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 and the unconverted tail oil of hydrocracking section are mixed into delayed coking unit 3 and carry out heat scission reaction and produce the coking dry gas at the bottom of the tower, liquefied gas, coking naphtha, coker gas oil, wax tailings and petroleum coke, temperature of reaction is 480 ℃, reaction pressure 0.17MPa.Coking naphtha wherein, coker gas oil, the benzoline of wax tailings and separation column 1, enter hydro-refining unit 4 after carbolic oil extraction plant 2 isolated dephenolize oil 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, the hydrocracking reaction product separation is dry gas, liquefied gas, hydrotreated naphtha, hydrogenated diesel oil and unconverted tail oil, hydrorefined average reaction temperature are 340 ℃, pressure 14.0MPa, volume space velocity 0.25h when hydrogen to oil volume ratio 1500: 1 and liquid
-1Volume space velocity 0.4h when 395 ℃ of the temperature of reaction of hydrocracking, pressure 14.0MPa, hydrogen to oil volume ratio 1000: 1 and liquid
-1Hydrobon catalyst is with alumina supporter, and the molybdenum oxide weight content is 15%, and the Tungsten oxide 99.999 weight content is 12%, and the nickel oxide weight content is 5%, and specific surface area is 185m
2/ g, pore volume are 0.35ml/g.(the silica/alumina molecular ratio is as 12 take 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 the cracking component, the Y zeolite weight content is 15%, the amorphous aluminum silicide weight content is 35%, and the Tungsten oxide 99.999 weight content is 28%, and the nickel oxide weight content is 8%, surplus is aluminum oxide, and specific surface area is 270m
2/ g, pore volume are 0.42ml/g.Hydrobon catalyst and hydrocracking catalyst carry out conventional prevulcanized before use to be processed.
Embodiment 3
The low-temperature pyrolysis coal tar of Shenmu County's brown coal, character sees Table 1, send to and enter vacuum fractionation tower 1 after pretreatment unit removes mechanical impurity and water, 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 and the unconverted tail oil of hydrocracking section are mixed into delayed coking unit 3 and carry out heat scission reaction and produce the coking dry gas at the bottom of the tower, liquefied gas, coking naphtha, coker gas oil, wax tailings and petroleum coke, temperature of reaction is 500 ℃, reaction pressure 0.17MPa.Coking naphtha wherein, coker gas oil, the benzoline of wax tailings and separation column 1, enter hydro-refining unit 4 after carbolic oil extraction plant 2 isolated dephenolize oil 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, the hydrocracking reaction product separation is dry gas, liquefied gas, hydrotreated naphtha, hydrogenated diesel oil and unconverted tail oil, hydrorefined temperature of reaction are 410 ℃, pressure 12.5MPa, volume space velocity 0.5h when hydrogen to oil volume ratio 2000: 1 and liquid
-1Volume space velocity 0.6h when 415 ℃ of the temperature of reaction of hydrocracking, pressure 11.0MPa, hydrogen to oil volume ratio 1400: 1 and liquid
-1Hydrobon catalyst is with alumina supporter, and the molybdenum oxide weight content is 15%, and the Tungsten oxide 99.999 weight content is 12%, and the nickel oxide weight content is 5%, and specific surface area is 185m
2/ g, pore volume are 0.35ml/g.(the silica/alumina molecular ratio is as 12 take 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 the cracking component, the Y zeolite weight content is 15%, the amorphous aluminum silicide weight content is 35%, and the Tungsten oxide 99.999 weight content is 28%, and the nickel oxide weight content is 8%, surplus is aluminum oxide, and specific surface area is 270m
2/ g, pore volume are 0.42ml/g.Hydrobon catalyst and hydrocracking catalyst carry out conventional prevulcanized before use to be processed.
Table 1 destructive distillation coal tar main character
| Raw material | Middle coalite tar |
| Density (20 ℃), g/cm 3 | 1.06 |
| Boiling range, ℃ | |
| 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 ℃), gcm -3 | 0.7576 |
| Boiling range, ℃ | |
| 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 oils and hydrocracking diesel fuel mixtures character
| Density (20 ℃), gcm -3 | 0.8684 |
| Boiling range, ℃ | |
| IBP/10％ | 163/210 |
| 30％/50％ | 222/236 |
| 70％/90％ | 254/287 |
| 95％/EBP | 305/342 |
| Viscosity (20 ℃), mm 2·s -1 | |
| Acidity, mgKOH (100mL) -1 | 1.57 |
| 10% steams excess carbon residue, % | ＜0.01 |
| Refractive power (20 ℃) | |
| Flash-point, ℃ | 55 |
| Condensation point, ℃ | ＜-50 |
| Cold filter clogging temperature, ℃ | ＜-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 the phenol products of the present invention: industrial phenol ctystallizing point is no less than 31 ℃ 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 ℃ before 190 ℃ of the 3 mixed cresols 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 ℃ before 205 ℃ of the technical xylenols, 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 heavy oil that obtains of middle coalite tar fractionation and the mixing oil of hydrocracking section unconverted oil.The operational condition that delayed coking unit adopts the results are shown in Table 3 with embodiment 2.
Table 3 delayed coking material balance
Claims (9)
1. coalite tar deep processing method in a kind is characterized in that comprising following processing step:
(1) with the fractionation of middle coalite tar raw material, obtains lighting end, carbolic oil, last running and heavy oil;
(2) carbolic oil that obtains of step (1) carries out phenol removal, obtains phenol products and dephenolize oil;
(3) heavy oil that obtains in the step (1) and hydrocracking section are produced unconverted tail oil mixing and are carried out pyrogenic reaction, obtain coking dry gas, liquefied gas, coking naphtha, coker gas oil, wax tailings and refinery coke product;
(4) at least a mixing in the dephenolize oil at least a and lighting end, last running and the step (2) that step (1) obtains in the coking naphtha, coker gas oil and the wax tailings that obtain of step (3), carry out hydrofining and hydrocracking reaction, reaction obtains dry gas, liquefied gas, hydrotreated naphtha and hydrogenated diesel oil product.
2. in accordance with the method for claim 1, it is characterized in that: carry out pre-treatment before the coalite tar fractionation in the step (1), pre-treatment removes moisture and mechanical impurity; Preferred described pre-treatment is centrifuging, electrodesalting and electrodehydrating.
3. in accordance with the method for claim 1, it is characterized in that: the vacuum fractionation tower is adopted in the middle low temperature coal tar raw material fractionation of step (1), cat head fractionates out lighting end, side line fractionates out carbolic oil, last running, obtain heavy oil at the bottom of the tower, the final boiling point of lighting end is not more than 180 ℃, and the final boiling point of carbolic oil is not more than 240 ℃, the final boiling point of last running is not more than 350 ℃, and the initial boiling point of heavy oil is not less than 340 ℃.
4. it is characterized in that in accordance with the method for claim 1: the described phenol removal of step (2) or step (4) adopts the soda acid method for extracting; Preferred described phenol removal adopts coal tar carbolic oil refining plant, and the phenol cut that contains that separation column is told enters extraction tower, adds alkaline solution in extraction tower, and the phenates that extracts is through steaming stripping oil, sulfuric acid or CO
2Obtain phenol products after decomposing, obtain dephenolize oil after extracting phenol products.
5. in accordance with the method for claim 1, it is characterized in that: the pyrogenic reaction operational condition described in the step (3) is 400 ℃～550 ℃ of temperature of reaction, reaction pressure 0.15MPa～0.5MPa; Be preferably 400 ℃～535 ℃ of temperature of reaction, reaction pressure 0.17MPa～0.35MPa.
6. in accordance with the method for claim 1, it is characterized in that: two-stage hydrocracking technique is adopted in the described hydrofining of step (4) and hydrocracking, the hydrofining reaction product is before entering hydrocracking reactor, at first enter separation column, the 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 the wax oil cut then carries out hydrocracking reaction.
7. according to claim 1 or 6 described methods, it is characterized in that: the hydrofining reaction condition in the step (4) is: the hydrofining reaction condition is: volume space velocity 0.15～1.5h when 180～427 ℃ of temperature of reaction, pressure 10.0～17.0MPa, hydrogen to oil volume ratio 500: 1～3500: 1 and liquid
-1Preferred reaction conditions is as follows: volume space velocity 0.2～1.2h when 180～420 ℃ of temperature of reaction, pressure 10.0～16.0MPa, hydrogen to oil volume ratio 800: 1～3000: 1 and liquid
-1
8. according to claim 1 or 6 described methods, it is characterized in that: the hydrocracking reaction condition in the step (4) is: volume space velocity 0.15～1.5h when 360～427 ℃ of temperature of reaction, pressure 10.0～17.0MPa, hydrogen to oil volume ratio 500: 1～2000: 1 and liquid
-1Preferred reaction conditions is as follows: volume space velocity 0.2～1.2h when 380～420 ℃ of temperature of reaction, pressure 10.0～16.0MPa, hydrogen to oil volume ratio 800: 1～1500: 1 and liquid
-1
9. according to claim 1 or 6 described methods, it is characterized in that: the hydrogen of hydrofining and hydrocracking process needs derives 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 the hydrogen from methyl alcohol in the step (4), and the concentrate of low-concentration hydrogen adopts the 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 |
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| CN103289718A (en) * | 2013-07-02 | 2013-09-11 | 西北大学 | Method for preparing dephenolized oil and phenolic resin through medium and low temperature coal tar oil |
| CN103695036A (en) * | 2013-12-31 | 2014-04-02 | 上海新佑能源科技有限公司 | Medium and low temperature coal tar processing method |
| CN104004541A (en) * | 2014-06-13 | 2014-08-27 | 煤炭科学研究总院 | Method for preparing coal-based high aromatic potential content raw oil |
| CN104178212A (en) * | 2013-05-20 | 2014-12-03 | 神华集团有限责任公司 | Coal tar hydrogenation upgrading method |
| CN105316034A (en) * | 2014-07-10 | 2016-02-10 | 神华集团有限责任公司 | Method for processing phenol-containing oil in coal tar |
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| CN104004541A (en) * | 2014-06-13 | 2014-08-27 | 煤炭科学研究总院 | Method for preparing coal-based high aromatic potential content raw oil |
| CN105316034A (en) * | 2014-07-10 | 2016-02-10 | 神华集团有限责任公司 | Method for processing phenol-containing oil in 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***集成技术股份有限公司 | A kind of processing system and its processing method of phenol tar |
| CN111704935A (en) * | 2020-08-03 | 2020-09-25 | 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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