CN115216341A - Medium-low temperature coal tar processing system and method - Google Patents
Medium-low temperature coal tar processing system and method Download PDFInfo
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- CN115216341A CN115216341A CN202110405792.0A CN202110405792A CN115216341A CN 115216341 A CN115216341 A CN 115216341A CN 202110405792 A CN202110405792 A CN 202110405792A CN 115216341 A CN115216341 A CN 115216341A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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Abstract
The invention discloses a system and a method for processing medium and low temperature coal tar. The system comprises a raw material flash evaporation unit, a gas-phase fraction hydrogenation unit, a liquid-phase fraction hydrogenation unit, a mixed hydrogen dissolving unit, a hydrogenation modification unit and a fractionation unit. The processing method comprises the following steps: (1) Hydrogen firstly enters a mixed hydrogen dissolving unit and then sequentially passes through a liquid phase fraction hydrogenation unit, a raw material flash evaporation unit and a gas phase fraction hydrogenation unit upwards; flashing the raw material into a gas phase fraction and a liquid phase fraction; (2) The gas phase fraction upwards enters a gas phase fraction hydrogenation unit for carrying out a shallow hydrogenation reaction, and a gas phase product enters a fractionation unit and is separated into a triphenyl raw material and a phenol raw material; and the liquid phase fraction enters a liquid phase fraction hydrogenation unit for hydrogenation reaction, and the liquid phase product enters a mixed hydrogen dissolving unit to form a hydrogen dissolving material flow for hydrogenation modification reaction. The invention efficiently converts medium-low temperature coal tar raw material into high-quality chemical raw material and fuel oil product under the conditions of low energy consumption and low hydrogen consumption.
Description
Technical Field
The invention belongs to the field of oil refining and chemical engineering, and particularly relates to a medium-low temperature coal tar processing system and a medium-low temperature coal tar processing method.
Background
The medium-low temperature coal tar is a component generated by coal pyrolysis at 500 to 900 ℃, and is characterized in that: the fraction is relatively light, the water and mechanical impurities are high, the H/C is high, and the phenols and chain hydrocarbons are high. The middle-low temperature coal tar fraction at the temperature of less than 180 ℃ mainly contains benzene, toluene, xylene and a small amount of alkane and olefin (mainly diolefin); in the fraction at 180 ℃, the acidic component accounts for about 30 percent (mainly comprising phenolic substances enriched at 170 to 230 ℃ and organic acid enriched at 190 to 330 ℃) and the neutral component accounts for 70 percent, and the neutral component has higher colloid and asphaltene contents. It can be seen that the properties of the medium-low temperature coal tar are obviously different from those of petroleum distillate oil, so that different processing modes are formed.
At present, the mature processing mode of medium-low temperature coal tar is mainly a hydrogenation route, and mainly comprises a pre-distillation-fixed bed hydrogenation technology, a hydrofining-hydrocracking reverse-order series technology, a fluidized bed-fixed bed combined technology, a delayed coking-fixed bed combined technology and the like. The pre-distillation-fixed bed hydrogenation technology only has a hydrofining process, so that the product has general properties; hydrofining-hydrocracking reverse-order tandem technology for avoiding water and NH generated in hydrofining process 3 The hydrocracking catalyst is affected so that hydrofinishing and hydrocracking takes place in two reactors. The combined technology of the fluidized bed and the fixed bed has high investment and complex process flow, while the combined technology of the delayed coking and the fixed bed has certain coke yield and cannot fully utilize coal tar resources.
Meanwhile, the technical route can also hydrogenate and saturate phenols with high content in the medium and low temperature coal tar. Phenol is widely applied to synthetic fibers, medicines, plasticizers and the like, and if phenol is removed through reaction, the hydrogen consumption of reaction chemistry is increased, and the added value and the product quality of products are reduced. And the phenol substances are produced, an extraction process needs to be added before hydrogenation. In addition, if the triphen substances in the light components of the medium and low temperature coal tar can be efficiently separated and utilized, the medium and low temperature coal tar products can be further developed in a diversified direction.
CN102465033A discloses a processing method of medium and low temperature coal tar, which separates phenolic substances by fractionation, acid-base extraction, pre-refining and refining methods and then processes dephenolized oil products. The method has complicated distillation range and needs to be provided with a plurality of distillation and reaction devices.
CN106635153A discloses a processing method of medium and low temperature coal tar whole fraction. The method adopts a process flow of coupling a slurry bed reactor containing a hydrocyclone and fixed bed hydrofining for strengthening heat and mass transfer.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a medium and low temperature coal tar processing system and a medium and low temperature coal tar processing method. The invention realizes the efficient conversion of medium-low temperature coal tar raw materials into high-quality chemical raw materials and fuel oil products under the conditions of low energy consumption and low hydrogen consumption by arranging different reaction zones in one reactor, changing the passing paths of different fractions of the medium-low temperature coal tar in the reactor and controlling reaction conditions, reaction types and product quality.
The medium-low temperature coal tar processing system comprises a raw material flash evaporation unit, a gas-phase fraction hydrogenation unit, a liquid-phase fraction hydrogenation unit, a mixed hydrogen dissolving unit, a hydrogenation modification unit and a fractionation unit; wherein the gas phase fraction hydrogenation unit, the raw material flash evaporation unit, the liquid phase fraction hydrogenation unit, the mixed hydrogen dissolving unit and the hydrogenation modification unit are sequentially arranged in the same reactor from top to bottom;
the raw material flash unit is used for flash evaporating the material entering the unit into a gas phase fraction and a liquid phase fraction; wherein the gas-phase fraction enters a gas-phase fraction hydrogenation unit, and the liquid-phase fraction enters a liquid-phase fraction hydrogenation unit; the gas-phase component is generally a fraction below 230 ℃, and the liquid-phase fraction is generally a fraction above 230 ℃; the material comprises a medium-low temperature coal tar raw material and gas-phase components from a liquid-phase fraction hydrogenation unit;
the gas-phase fraction hydrogenation unit is used for carrying out shallow refining and saturated diene reaction on gas-phase fractions (containing benzene, toluene and xylene enriched at the initial boiling point of 180-180 ℃ and phenolic substances enriched at the temperature of 180-230 ℃);
the liquid phase fraction hydrogenation unit is used for desulfurization, denitrification, aromatic saturation and deacidification reactions of the liquid phase fraction and the liquid phase components reflowing from the gas phase fraction hydrogenation unit.
The mixed hydrogen dissolving unit is used for mixing and dissolving the liquid-phase product of the liquid-phase fraction hydrogenation unit and hydrogen to form a hydrogen dissolving material flow; the mixed hydrogen dissolving unit is communicated with a hydrogen source, and mixed hydrogen dissolving components or equipment, such as a membrane tube type hydrogen dissolving component, a high-efficiency hydrogen mixer, a micro-bubble generator, a bubble separator and the like, are generally arranged in the mixed hydrogen dissolving unit;
the hydrogenation modification unit is used for hydrogenation modification pour point depression reaction of the hydrogen-dissolved material flow, mainly isomerization of macromolecular straight-chain alkane and saturation ring-opening reaction of aromatic hydrocarbon;
the fractionating unit is used for fractionating a gas-phase hydrogenation product obtained by the gas-phase fraction hydrogenation unit, cutting the product at 180 ℃ generally, and separating a triphenyl raw material and a phenol raw material, and generally taking the form of a fractionating tower; the fractionation unit is in communication with the top gas phase outlet of the reactor.
The invention also provides a medium and low temperature coal tar processing method, which comprises the following steps:
(1) Hydrogen firstly enters a mixed hydrogen dissolving unit of a reactor and then sequentially passes through a liquid phase fraction hydrogenation unit, a raw material flash evaporation unit and a gas phase fraction hydrogenation unit upwards; feeding the medium-low temperature coal tar raw material into a raw material flash evaporation unit in the reactor for flash evaporation to obtain gas phase fraction and liquid phase fraction;
(2) The gas phase fraction upwards enters a gas phase fraction hydrogenation unit for carrying out a shallow hydrogenation reaction, and the obtained gas phase hydrogenation reaction product is discharged from the top of the reactor and enters a fractionation unit to be separated into a triphenyl raw material and a phenol raw material; the liquid phase fraction flows downwards to enter a liquid phase fraction hydrogenation unit for hydrodesulfurization, denitrification, aromatic saturation and deacidification reactions, the liquid phase product of the reaction flows downwards to enter a mixed hydrogen dissolving unit, and is mixed and contacted with hydrogen to obtain a hydrogen dissolving material flow, and the hydrogen dissolving material flow enters a hydrogenation modification unit for hydrogenation modification reactions, and the liquid phase effluent is discharged from the bottom of the reactor.
In the method, the medium-low temperature coal tar raw material is generally subjected to dehydration and mechanical impurity removal treatment, the distillation range is generally 80 to 700 ℃, wherein the yield of fractions below 180 ℃ is not less than 10 percent, and the yield of fractions above 500 ℃ is not less than 20 percent. The water content is not more than 30 percent, and the N content is not more than 1 percent.
In the process of the present invention, the reactor is generally a fixed bed reactor.
In the method, the operating condition of the raw material flash unit is 3.0-8.0 MPa, preferably 4.0-6.0 MPa, wherein the hydrogen partial pressure accounts for 45-80% of the total pressure; the feeding temperature is 260 to 350 ℃, preferably 280 to 320 ℃.
In the method of the invention, the gas phase fraction hydrogenation unit is filled with a light distillate hydrogenation catalyst, which generally takes Mo-Ni or Mo-Co as the active metal of the catalyst and Al 2 O 3 The catalyst is a carrier, the metal loading is 15wt% -30 wt%, and a FH-40B catalyst developed by FRIPP is preferred. The filling volume proportion of the catalyst in the gas-phase fraction hydrogenation unit is 1-40%, preferably 5-20% based on the total filling amount of the catalyst in the reactor. The operating conditions of the gas phase fraction hydrogenation unit are generally: the pressure is 1.0 to 6.0MPa, preferably 2.0 to 4.0MPa, wherein the hydrogen partial pressure accounts for 40 to 70 percent of the total pressure; the volume airspeed is 0.1 to 10.0h -1 Preferably 0.5 to 6.0 hours -1 (ii) a The reaction temperature is 150 to 300 ℃, and preferably 180 to 220 ℃; hydrogen-oil volume ratio 10:1 to 400:1, preferably 100:1 to 200:1.
in the method, a hydrofining catalyst is filled in the liquid-phase fraction hydrogenation unit, mo-Ni or Mo-Co is generally used as a catalyst active metal, and Al 2 O 3 Is used as a carrier, and the metal loading amount is 20-30 wt%. FHUDS series catalysts, as developed by FRIPP, are preferred FHUDS-6, FHUDS-10 catalysts. The filling volume proportion of the catalyst in the liquid phase fraction hydrogenation unit is 1-80%, preferably 30-60%, based on the total filling amount of the catalyst in the reactor. The operating conditions of the liquid phase fraction hydrogenation unit are generally as follows: the pressure is 3.0 to 10.0MPa, preferably 5.0 to 8.0MPa, wherein the hydrogen partial pressure accounts for 50 to 90 percent of the total pressure; the volume airspeed is 0.1 to 10.0h -1 Preferably 0.5 to 3.0 hours -1 (ii) a The reaction temperature is 220 to 400 ℃, and preferably 300 to 360 ℃; hydrogen-oil volume ratio 10:1 to 500:1 preferably 100:1 to 400:1.
in the method, the mixed hydrogen dissolving unit is mainly used for providing a hydrogen inlet, and parameters such as hydrogen flow, temperature and the like are flexibly controlled, so that not only can the uplink hydrogen be fully contacted with the downlink liquid-phase component of the liquid-phase fraction hydrogenation unit and the mass transfer be strengthened, the reaction requirement of the liquid-phase fraction hydrogenation unit is met, but also the effects of stripping and removing impurities of the uplink hydrogen and carrying light components to the gas-phase fraction hydrogenation unit can be exerted. Particularly, the medium-low temperature coal tar raw material has a certain water content, and the acidic substance with higher content can be hydrogenated to generate water in the liquid phase fraction hydrogenation unit, which can cause great influence on the stability of the catalyst, and the hydrogen entering and ascending from the mixed hydrogen-dissolving unit can also effectively strip the water. The operation condition of the mixed hydrogen dissolving unit is 3.0 to 10.0MPa, preferably 5.0 to 8.0MPa, wherein the hydrogen partial pressure accounts for 100 percent of the total pressure; the feeding temperature is 30 to 400 ℃, and preferably 200 to 340 ℃. In the fresh hydrogen feeding, the proportion of the ascending hydrogen and the dissolved hydrogen under the standard condition is as follows: 1:1 to 10:1, preferably 3:1~6:1.
in the method of the invention, the hydro-upgrading unit is filled with hydro-upgrading pour point depressing catalyst, which generally takes W-Ni as catalyst active metal and Al 2 O 3 Is a carrier, and the metal loading is 20-30%. Such as FC-16 catalyst developed by FRIPP. The filling volume proportion of the catalyst of the hydro-upgrading unit is 1-50%, preferably 10-40% based on the total filling amount of the catalyst in the reactor. The operating conditions of the hydro-upgrading unit are generally: the pressure is 4.0 to 10.0MPa, preferably 6.0 to 8.0MPa, the reaction zone is a pure liquid phase reaction zone, and the volume ratio of standard hydrogen to oil is 1 to 300, preferably 100 to 200; the volume airspeed is 0.1 to 8.0h -1 Preferably 0.5 to 2.0 hours -1 (ii) a The reaction temperature is 200 to 400 ℃, preferably 280 to 360 ℃.
In the method, the liquid phase effluent discharged from the bottom of the reactor can be fractionated and cut according to the diesel fraction to be separated into the diesel blending component and the tail oil, and the tail oil is preferably recycled to the mixed hydrogen dissolving unit.
Compared with the prior art, the invention has the following advantages:
1. the medium-low temperature coal tar raw material is subjected to fraction cutting in a raw material flash evaporation unit, wherein triphen and phenol substances are enriched in components below 230 ℃, and saturated diene is subjected to shallow refining, so that the chemical raw material with high added value of the product is reserved, and the phenomenon that the diene enters other reaction zones along with the raw material and is coked and condensed at high temperature to affect long-period operation is avoided; polycyclic aromatic hydrocarbon and nitride are enriched in the liquid-phase component above 230 ℃, the hydrogen partial pressure in the liquid-phase fraction hydrogenation reaction unit below is high, the liquid-phase fraction hydrogenation reaction unit is a suitable hydrogenation reaction environment and is favorable for improving the reaction selectivity and the conversion rate, the refined liquid-phase component has high n-paraffin and aromatic hydrocarbon content, and after the mixed hydrogen-soluble zone unit is contacted with pure hydrogen, dissolved hydrogen is carried into the hydrogenation modification unit for hydrogenation modification condensation reduction reaction, so that the indexes of the diesel oil product, such as cetane number, condensation point and the like, are greatly improved. Meanwhile, the oil product flowing out of the reactor device does not need to be cooled to separate excessive hydrogen, and the heat exchange flow arrangement in the conventional technology is also omitted.
2. The hydrogen in the invention not only meets the chemical hydrogen consumption required by the reaction of each reaction zone, but also can flexibly adjust the inlet hydrogen amount according to the properties of raw materials and the requirements of products, and plays the roles of stabilizing the reaction phase state of each reaction zone, adjusting the partial pressure of the hydrogen and reducing the content of impurities. The hydrogen inlet is arranged in a gas-liquid mixing area below the liquid phase fraction hydrogenation unit, the proportion of the hydrogen ascending in a gas phase state and the hydrogen descending in a liquid phase state can be controlled by adjusting the operation conditions, and the hydrogen is in a gas phase in the gas phase fraction hydrogenation unit and in a liquid phase in the hydrogenation modification unit. Because the liquid phase fraction hydrogenation unit has higher requirement on hydrogen partial pressure, the position of a hydrogen inlet can meet the high hydrogen partial pressure in the region, and the deep denitrification and the optimization of saturated aromatic hydrocarbon reaction environment are facilitated. The liquid fraction hydrogenation unit is in countercurrent contact with the reaction raw material, and the gas phase components (including hydrogen, small molecular hydrocarbons and H) 2 S、NH 3 、H 2 O) and the like, and the materials going upwards and going downwards of the raw material flash evaporation unit are subjected to mass transfer and separation, so that the separation effect of light and heavy components in the raw materials can be enhanced, and simultaneously, the materials carry water and H generated by the reaction 2 S and NH 3 Quickly off the catalyst surface and out of the apparatus at the top of the reactor, avoiding its effect on catalyst strength and activity. Meanwhile, because the hydrogen amount is adjustable, the gas speed can be adjusted according to the change of the gasification rate and the liquid phase fraction of the raw materials in the reactor, thereby avoiding the phenomenon that the hydrogen amount is adjustableFlooding of the hydrocracking reaction zone occurs.
3. In the traditional gas-liquid-solid three-phase reaction, gas-phase hydrogen can reach the surface of a solid-phase catalyst only by penetrating liquid-phase raw oil, and the reaction efficiency is influenced due to diffusion limitation. The upper, middle and lower reaction zones are ingeniously arranged into a gas-solid reaction zone, a gas-liquid-solid reaction zone and a liquid-solid reaction zone, wherein a gas-phase fraction hydrogenation unit and a hydrogenation modification unit are subjected to two-phase reaction with higher mass transfer efficiency, and a gas-liquid phase reverse contact is adopted in the middle liquid-phase fraction hydrogenation unit, so that the gas-liquid mass transfer driving force is enhanced, and the reaction efficiency is integrally improved. Meanwhile, the three reaction zones provided by the invention can make the reaction system more stable. When the gas-liquid reverse contact in the liquid phase fraction hydrogenation unit strengthens the mass transfer process, along with back mixing, stable pressure control is needed, the uppermost gas phase fraction hydrogenation unit has a large compressible gas phase space, a good buffer effect is realized on the stable bed layer pressure and the stable fluid flowing state, the gas phase flow rate and the liquid layer thickness of the liquid phase fraction hydrogenation unit can be adjusted by flexibly controlling the outlet gas quantity, and the gas velocity range of flooding is enlarged. The lower hydro-upgrading unit is a liquid phase space, so that the outlet material flow state of the reactor can be well controlled, the problem that hydrogen is carried out of the reactor without passing through a catalyst bed layer to react is solved, a high-pressure separator in the conventional process flow can be omitted, and the flow is simplified. Meanwhile, the lower diesel oil hydrofining area is a liquid phase space, the outlet material flow state of the reactor can be well controlled, if the area is not existed, the problem that hydrogen is carried out of the reactor without reaction through a catalyst bed layer can be caused, and a high-pressure separator in the conventional process flow can be omitted, so that the flow is simplified.
Drawings
FIG. 1 is a schematic diagram of a medium and low temperature coal tar processing system and a processing method of the invention.
In the figure: 1-medium and low temperature coal tar raw material, 2-hydrogen, 3-gas phase fraction hydrogenation unit, 4-raw material flash evaporation unit, 5-liquid phase fraction hydrogenation unit, 6-mixed hydrogen dissolving unit, 7-hydrogenation modification unit, 8-first reaction product, 9-fractionation unit, 10-triphenyl raw material, 11-phenolic raw material and 12-second reaction product.
Detailed Description
The invention is explained in more detail below with reference to the drawing description and the examples, without thereby restricting the invention.
The implementation process of the medium and low temperature coal tar processing method of the invention is illustrated by taking the attached figure 1 as an example: and (3) feeding the medium-low temperature coal tar raw material 1 into a raw material flash evaporation unit of a fixed bed hydrogenation reactor, and performing flash evaporation separation to obtain gas phase fraction and liquid phase fraction. The gas phase fraction flows upward to enter the gas phase fraction hydrogenation unit 3, and the liquid phase fraction flows downward to enter the liquid phase fraction hydrogenation unit 5. The hydrogen 2 enters a mixed hydrogen dissolving unit 6 of the hydrogenation reactor (the mixed hydrogen dissolving unit 6 is provided with mixed hydrogen dissolving equipment), and after being mixed and contacted with the liquid phase material flowing downwards in the liquid phase fraction hydrogenation unit 5, the hydrogen flows upwards to enter the liquid phase fraction hydrogenation unit 5, the liquid phase material carrying the hydrogen flows downwards to enter a hydrogenation modification unit 7 for hydrogenation modification reaction, and after a second reaction product 12 flows out of the reactor, the second reaction product is fractionated and cut according to diesel oil fraction to be separated into diesel oil blending components and tail oil.
Wherein, a gas phase reaction is generated in the gas phase fraction hydrogenation unit 3, a diene saturation reaction of fractions below 230 ℃ is mainly generated, a first reaction product 8 is generated, and the first reaction product enters a fractionation unit 9 to be separated into a triphenyl raw material 10 and a phenolic raw material 11.
The liquid phase fraction hydrogenation unit 5 generates gas-liquid two-phase reaction, the liquid phase is that the fraction with the temperature of more than 230 ℃ in the medium-low temperature coal tar flows downwards, the gas phase is that hydrogen flows upwards, and the gas-liquid reverse contact generates deep hydrodesulfurization, denitrification, aromatic saturation and deacidification reaction. H formed by reaction 2 S、NH 3 、H 2 O and low molecular hydrocarbons flow upward with the gas phase stream and flow out of the top of the reactor.
The hydrogen mixing and dissolving equipment is partially or completely positioned in a liquid phase environment, hydrogen feeding is positioned below the liquid level and is sprayed into the liquid phase of the hydrogen mixing and dissolving equipment through porous equipment, the gas phase in the hydrogen mixing and dissolving equipment rapidly flows and is tangent to the liquid phase, the effect of full mixing is achieved, the content of hydrogen in the liquid phase reaches a certain solubility, the liquid phase after hydrogen mixing downwards enters a hydrogenation and modification unit, and excessive hydrogen is gathered into a continuous gas phase and upwards enters a liquid phase fraction hydrogenation unit. The hydrogen flow rate to the liquid phase fraction hydrogenation unit can be adjusted by the hydrogen injection amount.
The hydrogenation modification unit 7 is a liquid phase reaction, namely hydrogenation modification of polycyclic aromatic hydrocarbon and isomerization pour point depression reaction of long-chain normal paraffin.
Example 1~3
In this embodiment, a 100mL fixed bed hydrogenation reactor is adopted, and a gas phase fraction hydrogenation unit, a liquid phase fraction hydrogenation unit and a hydrogenation modification unit from top to bottom are all provided with a catalyst bed layer. And a high-efficiency hydrogen mixer is arranged in the hydrogen mixing and dissolving unit between the liquid phase fraction hydrogenation unit and the hydrogenation and modification unit. The hydrogen mixer is partially or completely positioned in a liquid phase environment, hydrogen feeding is positioned below the liquid level and is sprayed into the liquid phase of the hydrogen mixer through porous equipment, the gas phase in the hydrogen mixer rapidly flows and is tangent to the liquid phase, the effect of full mixing is achieved, the content of hydrogen in the liquid phase reaches a certain solubility, the liquid phase after hydrogen mixing downwards enters a hydrogenation and modification unit, and excessive hydrogen is gathered into continuous gas phase and upwards enters a liquid phase fraction hydrogenation unit. The hydrogen flow rate to the liquid phase fraction hydrogenation unit can be adjusted by the hydrogen injection amount. In this embodiment, by controlling the amount of hydrogen at the inlet, the ratio of the upward hydrogen to the dissolved hydrogen under standard conditions is 1:1. a Mo-Co type light distillate oil hydrogenation catalyst A is filled in a gas phase fraction hydrogenation unit, a Ni-Mo type hydrofining catalyst B is filled in a liquid phase fraction hydrogenation unit, and a Ni-W type hydro-upgrading isomerization pour point depressing catalyst C is filled in a hydro-upgrading unit. The volume filling ratio of the catalyst according to the volume of the reactor A: b: c =20:40:40. the medium-low temperature coal tar subjected to dehydration and mechanical impurity removal treatment is used as a raw material. The catalyst properties are shown in Table 1, the feedstock properties are shown in Table 2, and the reaction process conditions and results are shown in Table 3.
Comparative example 1
By adopting the existing pre-distillation-fixed bed hydrogenation technology, heavy component tailing of the raw materials is carried out in a distillation tower, then the raw materials are introduced into a 100mL pilot hydrogenation device, and products enter a fractionating tower to obtain naphtha, diesel oil and tail oil. The raw materials were the same as in example, and Ni-Mo type hydrofinishing catalyst B was packed in a volume equivalent to the sum of the three catalysts A, B, C in example 1~3, and the reaction conditions were the same as in the liquid phase fraction hydrogenation unit of example 3.
Comparative example 2
The prior hydrofining-hydrocracking reverse-order series technology is adopted. A100 mL fixed bed hydrofinishing reactor 1 and a 100mL fixed bed hydrocracking reactor 2 were provided, respectively. The raw material firstly enters a hydrofining reactor, and then enters a fractionating tower to be separated into naphtha, diesel oil and tail oil, and the tail oil enters a hydrocracking reactor and then enters the hydrofining reactor together with a fresh raw material. The same raw material properties as in example, 50mL of catalyst B was charged in the hydrofinishing reactor, and 50mL of catalyst C was charged in the hydrocracking reactor. The reaction conditions of the two reactors were the same as those of the liquid phase fraction hydrogenation unit of example 3.
TABLE 1 physicochemical Properties of the catalyst
TABLE 2 Properties of the feed oils
TABLE 3 hydrogenation process conditions and results
TABLE 3 (continuous) hydrogenation Process conditions and results
It can be seen from table 3 that, compared with comparative examples 1 and 2, the invention can process medium and low temperature coal tar raw materials by using a simpler reaction process, and can directly produce phenols and triphenyl raw materials by controlling the cut of 230 ℃ and further fractionating, while the two comparative examples need to be provided with a special extraction process to separate the phenols raw materials. Meanwhile, the invention realizes the intensified mass transfer in the three reaction zones, thereby achieving better reaction effect under the same reaction condition and higher product quality. Compared with the pre-distillation-fixed bed technology, the cetane number of the diesel oil is obviously improved; compared with the hydrofining-hydrocracking reverse-order series technology, the sulfur content and cetane index of the invention also have obvious advantages. Due to the deep coupling of the three reaction zone environments and the adjustable hydrogen amount, the device is always in a stable state in the test process, the product quality is always qualified, and the flooding phenomenon is not generated.
Claims (18)
1. A medium and low temperature coal tar system of processing which characterized in that: the system comprises a raw material flash evaporation unit, a gas-phase fraction hydrogenation unit, a liquid-phase fraction hydrogenation unit, a mixed hydrogen dissolving unit, a hydrogenation modification unit and a fractionation unit; wherein the gas phase fraction hydrogenation unit, the raw material flash evaporation unit, the liquid phase fraction hydrogenation unit, the mixed hydrogen dissolving unit and the hydrogenation modification unit are sequentially arranged in the same reactor from top to bottom;
the raw material flash unit is used for flash evaporating the material entering the unit into a gas phase fraction and a liquid phase fraction; wherein the gas-phase fraction enters a gas-phase fraction hydrogenation unit, and the liquid-phase fraction enters a liquid-phase fraction hydrogenation unit;
the gas-phase fraction hydrogenation unit is used for carrying out shallow refining and saturated diene reaction on the gas-phase fraction;
the liquid phase fraction hydrogenation unit is used for desulfurization, denitrification, aromatic saturation and deacidification reactions of the liquid phase fraction and the liquid phase components reflowing from the gas phase fraction hydrogenation unit;
the mixed hydrogen dissolving unit is used for mixing and dissolving the liquid-phase product of the liquid-phase fraction hydrogenation unit and hydrogen to form a hydrogen dissolving material flow;
the hydro-upgrading unit is used for hydro-upgrading pour point depressing reaction of the hydrogen-dissolved material flow.
2. The fractionating unit is used for fractionating gas-phase hydrogenation products obtained by the gas-phase fraction hydrogenation unit.
3. The processing system of claim 1, wherein: the gas-phase component is a fraction below 230 ℃, and the liquid-phase component is a fraction above 230 ℃; the material comprises a medium-low temperature coal tar raw material and gas-phase components from a liquid-phase fraction hydrogenation unit.
4. The processing system of claim 1, wherein: the mixed hydrogen dissolving unit is communicated with a hydrogen source, and a mixed hydrogen dissolving assembly or equipment is arranged in the mixed hydrogen dissolving unit.
5. The processing system of claim 3, wherein: the mixed hydrogen dissolving component or equipment comprises a membrane tube type hydrogen dissolving component, a high-efficiency hydrogen mixer, a micro-bubble generator and a bubble splitter.
6. The processing system of claim 1, wherein: the processing system of claim 1, wherein: the fractionating unit is used for fractionating a gas-phase hydrogenation product obtained by the gas-phase fraction hydrogenation unit, and cutting and separating a triphenyl raw material and a phenol raw material at 180 ℃; the fractionation unit is in communication with the top gas phase outlet of the reactor.
7. The medium and low temperature coal tar processing method is characterized by comprising the following steps: (1) Hydrogen firstly enters a mixed hydrogen dissolving unit of a reactor and then sequentially passes through a liquid phase fraction hydrogenation unit, a raw material flash evaporation unit and a gas phase fraction hydrogenation unit upwards; feeding the medium-low temperature coal tar raw material into a raw material flash evaporation unit in the reactor to be flashed into gas phase fraction and liquid phase fraction; (2) The gas phase fraction upwards enters a gas phase fraction hydrogenation unit for carrying out a shallow hydrogenation reaction, and the obtained gas phase hydrogenation reaction product is discharged from the top of the reactor and enters a fractionation unit to be separated into a triphenyl raw material and a phenol raw material; the liquid phase fraction flows downwards to enter a liquid phase fraction hydrogenation unit for hydrodesulfurization, denitrification, aromatic saturation and deacidification reactions, the liquid phase product of the reaction flows downwards to enter a mixed hydrogen-dissolving unit, the mixed hydrogen-dissolving unit is mixed with hydrogen to obtain a hydrogen-dissolved material flow, the hydrogen-dissolved material flow enters a hydrogenation modification unit for hydrogenation modification reaction, and the liquid phase effluent is discharged from the bottom of the reactor.
8. The method of claim 6, wherein: the medium and low temperature coal tar raw material is subjected to dehydration and mechanical impurity removal treatment, the distillation range is 80 to 700 ℃, wherein the yield of fractions below 180 ℃ is not less than 10 percent, and the yield of fractions above 500 ℃ is not less than 20 percent.
9. The water content is not more than 30 percent, and the N content is not more than 1 percent.
10. The method of claim 6, wherein: the operating condition of the raw material flash unit is 3.0-8.0 MPa, preferably 4.0-6.0 MPa, wherein the hydrogen partial pressure accounts for 45-80% of the total pressure; the feeding temperature is 260 to 350 ℃, preferably 280 to 320 ℃.
11. The method of claim 6, wherein: the gas phase fraction hydrogenation unit is filled with a light distillate oil hydrogenation catalyst; the filling volume proportion of the catalyst in the gas-phase fraction hydrogenation unit is 1-40% based on the total filling amount of the catalyst in the reactor.
12. The method of claim 6, wherein: the operating conditions of the gas-phase fraction hydrogenation unit are as follows: the pressure is 1.0 to 6.0MPa, preferably 2.0 to 4.0MPa, wherein the hydrogen partial pressure accounts for 40 to 70 percent of the total pressure; the volume airspeed is 0.1 to 10.0h -1 Preferably 0.5 to 6.0 hours -1 (ii) a The reaction temperature is 150 to 300 ℃, preferably 180 to 220 ℃; hydrogen-oil volume ratio 10:1 to 400:1, preferably 100:1 to 200:1.
13. the method of claim 6, wherein: a hydrofining catalyst is filled in the liquid fraction hydrogenation unit; the filling volume proportion of the catalyst in the liquid phase fraction hydrogenation unit is 1-80%, preferably 30-60%, based on the total filling amount of the catalyst in the reactor.
14. The method of claim 6, wherein said at least one of said first and second sets of parameters is selected from the group consisting of,the method is characterized in that: the operating conditions of the liquid phase fraction hydrogenation unit are as follows: the pressure is 3.0 to 10.0MPa, preferably 5.0 to 8.0MPa, wherein the hydrogen partial pressure accounts for 50 to 90 percent of the total pressure; the volume airspeed is 0.1 to 10.0h -1 Preferably 0.5 to 3.0 hours -1 (ii) a The reaction temperature is 220 to 400 ℃, and preferably 300 to 360 ℃; hydrogen-oil volume ratio 10:1 to 500:1 preferably 100:1 to 400:1.
15. the method of claim 6, wherein: the operation condition of the mixed hydrogen dissolving unit is 3.0 to 10.0MPa, preferably 5.0 to 8.0MPa, wherein the hydrogen partial pressure accounts for 100 percent of the total pressure; the feeding temperature is 30 to 400 ℃, and preferably 200 to 340 ℃; in the fresh hydrogen feeding, the proportion of the ascending hydrogen and the dissolved hydrogen under the standard condition is as follows: 1:1 to 10:1, preferably 3:1~6:1.
16. the method of claim 6, wherein: the hydrogenation modification unit is filled with a hydrogenation modification pour point depressing catalyst; the filling volume ratio of the catalyst in the hydro-upgrading unit is 1-50%, preferably 10-40% based on the total filling amount of the catalyst in the reactor.
17. The operating conditions of the hydro-upgrading unit are generally: the pressure is 4.0 to 10.0MPa, preferably 6.0 to 8.0MPa, the reaction zone is a pure liquid phase reaction zone, and the volume ratio of standard hydrogen to oil is 1 to 300, preferably 100 to 200; the volume airspeed is 0.1 to 8.0h -1 Preferably 0.5 to 2.0 hours -1 (ii) a The reaction temperature is 200 to 400 ℃, preferably 280 to 360 ℃.
18. The method of claim 6, wherein: and (3) fractionating the liquid phase effluent discharged from the bottom of the reactor, cutting according to diesel oil fraction, separating into diesel oil blending components and tail oil, and preferably recycling the tail oil to the mixed hydrogen dissolving unit.
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| CN116445192A (en) * | 2023-04-25 | 2023-07-18 | 西北大学 | Method for preparing coal-based heat-absorbing hydrocarbon fuel by taking coal tar and naphthalene oil as raw materials |
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| CN101343563A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Hydrotreating process for light hydrocarbons |
| CN102876367A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Deep desulphurization dearomatization combination method of diesel oil |
| US20190345399A1 (en) * | 2018-05-11 | 2019-11-14 | Inner Mongolia ShengYuan Technology Co. Ltd. | Combined Hydrogenation Process Method for Producing High-Quality Fuel by Medium-Low-Temperature Coal Tar |
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| CN101343563A (en) * | 2007-07-09 | 2009-01-14 | 中国石油化工股份有限公司 | Hydrotreating process for light hydrocarbons |
| CN102876367A (en) * | 2011-07-11 | 2013-01-16 | 中国石油化工股份有限公司 | Deep desulphurization dearomatization combination method of diesel oil |
| US20190345399A1 (en) * | 2018-05-11 | 2019-11-14 | Inner Mongolia ShengYuan Technology Co. Ltd. | Combined Hydrogenation Process Method for Producing High-Quality Fuel by Medium-Low-Temperature Coal Tar |
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| CN116445192A (en) * | 2023-04-25 | 2023-07-18 | 西北大学 | Method for preparing coal-based heat-absorbing hydrocarbon fuel by taking coal tar and naphthalene oil as raw materials |
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Effective date of registration: 20231220 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |