CN104711020A - Coal tar multistage hydrogenation technology - Google Patents

Coal tar multistage hydrogenation technology Download PDF

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Publication number
CN104711020A
CN104711020A CN201310675395.0A CN201310675395A CN104711020A CN 104711020 A CN104711020 A CN 104711020A CN 201310675395 A CN201310675395 A CN 201310675395A CN 104711020 A CN104711020 A CN 104711020A
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reaction
hydrogen
coal tar
reactor
reaction zone
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CN104711020B (en
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关明华
全辉
孙国权
姚春雷
赵威
张志银
林振发
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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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
    • C10G67/14—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 at least two different refining steps in the absence of hydrogen
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/205—Metal content

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a coal tar multistage hydrogenation technology, and belongs to the technical field of coal chemical industry. In the provided technology, low-middle temperature coal tar whole fraction is pumped into an electric desalination unit; after the electric desalination, the coal tar is transferred to a flash evaporation fractionating tower; the material from the bottom of the tower is transferred to a fluidized bed reactor to carry out hydrogenation pretreatment reactions; the effluent of the pretreatment is separated, the liquid fraction and hydrogen gas carry out hydrogenation refining reactions, the product of the hydrogenation refining reactions is transferred to a hydrogenation cracking reactor to perform hydrogenation cracking reactions; the effluent is separated to obtain naphtha and diesel oil, and the unconverted oil is returned to the hydrogenation refining reactor. Compared to the prior art, the provided technology can guarantee the long-term and stable operation of equipment and achieve the high efficient utilization of coal tar.

Description

A kind of coal tar multistage hydrogenation treatment technique
Technical field
The present invention relates to a kind of coal tar multistage hydrogenation treatment technique, particularly with dead oil or full cut for raw material, adopt multi-stek hydrogenation explained hereafter to clean the processing method of light Fuel.
Background technology
Coal tar is the by product of coal coking, destructive distillation and gasification.Coal tar is the product liquid obtained in the dry distillation of coal and gasification, its output is closely bound up with the metallurgical industry development that waits, China's metallurgical cokes in 2007 and semicoke output are respectively 3.3 hundred million tons and 2,050 ten thousand tons, corresponding coal tar output about 1,230 ten thousand tons, can reach 5,000 ten thousand tons according to coal clean utilization planning estimation medium-long term; Coal tar output has reached fairly large, the treatment technology that exploitation is suitable and work flow, all has positive effect to resources effective utilization, minimizing environmental pollution, supplementary petroleum resources deficiency.
Coal tar is different from natural oil, have that boiling point is high, high-density, heteroatoms are many, Sauerstoffatom is high, high carbon residue, H/C be than low, metal content high, difficulty of processing is comparatively large, based on the singularity of coal tar character, must carry out pre-treatment workshop section before entering fixed bed hydrogenation device; Through pretreated coal tar by selecting suitable hydrofining and hydrocracking catalyst, adopt suitable technical process by the complete lighting of full cut coal tar fraction.
In ZL02122573.7, be full fraction of coal tar is first removed through flash distillation be less than C 5after lighter hydrocarbons, then carry out pre-hydrofining by 4 switch protecting reactors, then enter boiling bed hydrogenation reactor, at MoO 3-W0 3-NiO-P-TiO 2under catalyst action, hydrogenator inlet pressure is not more than 15.0MPa (hydrogen dividing potential drop), and initial reaction temperature is 300-390 DEG C (beds medial temperature), volume space velocity 0.4-4.0h -1, hydrogen-oil ratio 500-3000Nm 3/ m 3.This production method is actual is fixed bed and ebullated bed process integration process, but because in tar, foreign matter content is high, and react easy coking under the high temperature conditions, cause beds choking phenomenon serious, keep long-term operation, often need more catalyst changeout, catalyst levels is large, add cost, make complex process.In addition switch the water that reactor product out contains a great deal of, unprocessedly directly enter hydrogenator, very large to catalyzer (catalyzer especially containing molecular sieve) activity influence, catalyst activity can be caused greatly to reduce.
CN1676583A describes hydrogenation of high temperature coal tar process in one.Technological process is: middle coal-tar heavy oil is heated to 250-300 DEG C through process furnace, hydrofining reactor is mixed into hydrogen, the refining oil that generates is through water distilling apparatus, fractionate out gasoline, diesel oil, lubricating oil and hydrogenation tail oil, hydrogenation tail oil is after the heating of cracking process furnace, enter cracking case after mixing with hydrogen, produce petrol and diesel oil cut further.This technique coal tar directly enters high-temperature heater can cause tube coking, affects the normal operation cycle of device.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of multistage coal tar hydrogenation process, the inventive method can the long-term operation of assurance device.
A kind of coal tar multistage hydrogenation treatment technique of the present invention comprises following content:
A) overhead components that coal tar raw material and step b) obtain is mixed, and after heat exchange, remove raw materials pretreatment (electric desalting) unit, remove the water, inorganic chlorine ion and the metallic impurity that contain in coal tar raw material;
B) logistics after step a) desalination enters flash distillation separation column, and isolated overhead components directly goes without cooling to mix with the foreign coal tar stock of step a), to reduce mixed rear stock oil density and viscosity;
C), after logistics out at the bottom of step b) flash distillation separation column tower mixes with hydrogen, after process furnace heating, enter boiling bed hydrogenation reactor, carry out weighted BMO spaces reaction;
D) reaction effluent that step c) obtains enters separator and carries out gas-liquid separation and fractionation, obtains hydrogen-rich gas, carburet hydrogen, product liquid and residue;
E) hydrogen-rich gas that step d) obtains uses through purifying treatment Posterior circle, after step d) gained product liquid mixes with hydrogen, enters hydrofining reactor and carries out hydrofining reaction;
F) step e) obtains reaction effluent and enters hydrocracking reactor, under hydrocracking catalyst and hydrogen exist, carry out hydrocracking reaction;
G) step f) obtains reaction effluent and is separated, and liquid obtains petroleum naphtha component, diesel component and unconverted oil through fractionation.
In coal tar hydrogenating process of the present invention, wherein in step a), described coal tar is the product liquid that coal obtains through pyrogenic reaction.In the present invention, coal tar raw material is middle coalite tar preferably.Described middle coalite tar nitrogen content is generally 1500 more than μ g/g, is preferably 2500 more than μ g/g, most preferably is 2500 ~ 15000 μ g/g.The initial boiling point of coal tar raw material is generally 160 ~ 450 DEG C, and be preferably 300 ~ 420 DEG C, final boiling point is generally 500 ~ 750 DEG C.Said pretreatment unit is electric desalting apparatus, generally carries out three grades of electric desalting, to remove the metallic impurity such as water, inorganic chlorine ion and sodium, calcium, magnesium, iron contained in coal tar raw material, require de-after stock oil salts contg lower than 3ppm.
In step a), the overhead components that general control coal tar raw material and step b) obtain mixed 20 DEG C density stabilized at 0.800 ~ 0.960g/cm 3between, preferably control at 0.850 ~ 0.900g/cm 3.
Wherein the said deep fat of thermal source that provides of step a) can be pretreatment unit or the reacted component loops logistics of hydrocracking section, or other the petroleum fractions after process furnace heating, if boiling spread is 100 ~ 300 DEG C of petroleum fractionss.
In coal tar hydrogenating process of the present invention, wherein in step b), after the logistics after step a) desalination is first filtered, then enter flash distillation separation column.Or in step c), step b) flash distillation separation column obtains tower base stream and entering boiling bed hydrogenation reactor again after strainer.
Boiling bed hydrogenation reactor described in step c) is the conventional ebullated bed reactor of this area.This reactor configurations has usual liquid phase circulation system, flow distribution system, catalyst material position monitoring system, catalyzer to add/heat-extraction system etc. online.Be filled with boiling-bed catalyst in described boiling bed hydrogenation reactor, described catalyzer is special bar shaped catalyst.Catalyzer composition comprises molybdenum oxide 1% ~ 10%, nickel oxide 0.1% ~ 5% by weight percentage, and can contain conven-tional adjuvants in catalyzer, all the other are the refractory oxide such as silicon-containing alumina or aluminum oxide carrier.The pore volume of boiling-bed catalyst is 0.40 ~ 0.42mL/g, and specific surface area is 170 ~ 180m 2/ g.
In coal tar hydrogenating process of the present invention, the processing condition of the boiling bed hydrogenation reactor described in step c) are generally: reaction pressure 12 ~ 20MPa, average reaction temperature: 380 ~ 400 DEG C, hydrogen to oil volume ratio 500 ~ 1000, fresh feed volume space velocity is 0.1 ~ 10.0h -1.Step d) gained product liquid do general control 450 ~ 550 DEG C, be preferably 470 ~ 530 DEG C.The boiling bed hydrogenation reactor that residue loops back step c) is obtained in step d).
Hydrofining reactor described in step e) adopts the conventional fixed-bed reactor of this area.Namely stock oil flows through hydrogenation catalyst bed from top to bottom.The catalyzer selected is conventional hydro catalyst for refining, described Hydrobon catalyst is made up of carrier and the hydrogenation metal component be loaded on carrier, catalyzer to comprise in the periodic table of elements group VIB active metal component in metal oxide weight 8% ~ 35%, and the VIIIth race's active metal component in metal oxide weight 1% ~ 7%, can contain conven-tional adjuvants in catalyzer, all the other are the refractory oxide such as silicon-containing alumina or aluminum oxide carrier.Catalyzer pore volume is for being not less than 0.32mL/g, and specific surface is for being not less than 160m 2/ g.The carrier that Hydrobon catalyst uses is inorganic refractory oxide, as aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc.
The inventive method, wherein in step e), can select stock oil and hydrogen and stream passes downwardly through the conventional flowsheet of Hydrobon catalyst bed.In the present invention in step e), hydrofining reactor is recommended to adopt following technical process: hydrofining reactor comprises the gas and liquid flowing reaction zone on top and the gas-liquid counter current reaction zone of bottom, first the product liquid that step d) obtains enters with hydrogen and flows reaction zone, and flows reaction zone use Hydrobon catalyst; And flow reaction effluent and enter middle gas-liquid separation zone and be separated, gas draws reactor; Liquid then enters the counter-flow reaction zone of bottom, and the hydrogen introduced with reactor bottom carries out counter current contact reaction.
In the inventive method, special recommendation and flow in reaction zone to use there is the catalyzer of following character: the average pore diameter of catalyzer is 7.5 ~ 9.5nm, preferably 8 ~ 9nm; The volume fraction that the pore volume in the hole of bore dia 4 ~ 10nm accounts for total pore volume is 70% ~ 90%, is preferably 75% ~ 85%; The pore volume in <4nm hole accounts for less than 5% of total pore volume.The catalyzer with this character is generally the catalyzer being prepared carrier production by chloride process, and the maturing temperature of catalyzer is generally at about 480 DEG C.And in counter-flow reaction zone the catalyzer of the following character of recommendation: the average pore diameter of catalyzer is 4 to being less than 7.5nm, preferably 5 ~ 7nm; Its median pore diameter is the volume fraction that the pore volume in the hole of 4 ~ 10nm accounts for total pore volume is 50 ~ 75%, preferably 55 ~ 65%; The pore volume in the hole of <4nm accounts for the volume fraction of total pore volume generally lower than 10%.Wherein with and flow compared with the catalyst for refining in reaction zone, the average pore diameter of counter-flow reaction zone Hydrobon catalyst used wants little 0.5 ~ 3nm, preferably little 1.0 ~ 2.5nm; The hole of aperture 4 ~ 10nm accounts for little 10 ~ 30 percentage ratios of volume fraction of total pore volume, preferably little 15 ~ 25 percentage ratios.The catalyzer used in counter-flow reaction zone be generally by sulphate as Tai-Ace S 150 method prepare carrier produce catalyzer, the maturing temperature of catalyzer is generally at about 450 DEG C.
In the inventive method, and the denitrification percent general control flowing reaction zone is 20wt% ~ 90wt%, preferably controls as 30wt% ~ 80wt%.And the processing condition flowing reaction zone are generally: average reaction temperature is 250 ~ 500 DEG C, be preferably 300 ~ 440 DEG C; Reaction pressure is 5.0 ~ 20.0MPa, is preferably 8.0 ~ 17.0MPa; Hydrogen to oil volume ratio is 100:1 ~ 4000:1, is preferably 400:1 ~ 2000:1; During liquid, volume space velocity is 1.0 ~ 10.0h -1, be preferably 1.0 ~ 4.0h -1.The processing condition of counter-flow reaction zone are generally: average reaction temperature is 250 ~ 500 DEG C, are preferably 300 ~ 440 DEG C; Reaction pressure is 5.0 ~ 20.0MPa, is preferably 8.0 ~ 17.0MPa; Hydrogen to oil volume ratio is 100:1 ~ 2000:1, is preferably 400:1 ~ 1000:1; During liquid, volume space velocity is 1.0 ~ 10.0h -1, be preferably 1.0 ~ 4.0h -1.
The said hydrocracking section of step f) uses fixed-bed reactor, and the catalyzer of selection is conventional hydrocracking catalyzer.Hydrocracking catalyst composition is by weight percentage: molybdenum oxide 5% ~ 25%, nickel oxide 1% ~ 10%, can contain conven-tional adjuvants, and all the other are the refractory oxide such as silicon-containing alumina or aluminum oxide carrier.Catalyzer pore volume is for being more than or equal to 0.25mL/g, and specific surface is for being more than or equal to 260m 2/ g.
The reaction conditions of the fixed bed hydrogenation cracking reaction described in step f) is: reaction pressure 12 ~ 20MPa, medial temperature 380 ~ 430 DEG C, hydrogen to oil volume ratio 800 ~ 1500, and during liquid, volume space velocity is 0.1 ~ 5.0h -1.
The said gas-liquid separation of step g) is carried out in tripping device.Described tripping device generally comprises high-pressure separator, light pressure separator etc.
Coal tar is that a kind of character is poor, condensed-nuclei aromatics, and resin and asphalt content is high, and mechanical impurity, metal content (especially iron and calcium), the non-natural oil product that oxygen level is very high, its processing can not simply apply mechanically the processing scheme used in existing refining of petroleum.The metallic impurity such as the water contained in coal tar raw material, inorganic chlorine ion and sodium, calcium, magnesium, iron are poisoning and corrosion of equipment is very serious to subsequent catalyst, these materials are dispersed in coal tar, be difficult to adopt usual method to remove, then easily there is fouling and the active centre of covering catalyst in these materials in hydrofining, hydrocracking catalyst.Find through research, by coal tar after electric desalting process, these materials being difficult to remove tentatively simply remove.The inventive method, by the burnt oil composition of Study on Coal and character, have selected suitable coal tar processing method, can the steady running of assurance device long period, realizes the utilization of the high yield of tar resource.
Specifically, coal tar hydrogenating process of the present invention has the following advantages:
1, in the prior art, coal tar desalination generally needs adding the laggard line operate of emulsion splitter, metal remover and water filling, complex operation and desalting effect is not good.The present inventor is found by research, after being mixed by coal tar, controls the suitable density of mixture and viscosity, just can well meet the requirement of electric desalting operation with part light hydrocarbon component.And material after desalination is by after flash separation, namely obtains the coal tar after desalination, flashing tower obtains overhead components and can reclaim with recycle simultaneously.
2, boiling bed hydrogenation-fixed bed hydrogenation combination process is adopted, be different from prior art and first carry out pretreated technique by distillation, the inferior coal pitch being difficult to utilize because distillation pretreatment technology produces can be avoided, thus the yield losses of the course of processing can be reduced, and realize the utilization of the high yield of tar resource.Simultaneously owing to adopting boiling bed hydrogenation technique, the running life of pretreatment unit can be improved.
3, through the pretreated full fraction of coal tar of ebullated bed comparatively high temps, its metal and oxygen level significantly reduce, and the high content nitrogen simultaneously also has part to reduce.Especially, a large amount of solid dusts in coal tar raw material obtain good removal, again after the process that fixed bed hydrogenation is refined with hydrocracking process, petroleum naphtha and the diesel oil distillate of quality product requirement can be met, achieve the efficiency utilization of coal tar raw material.
Although 4 the inventive method comprise coal tar boiling bed hydrogenation pre-treatment step, the nitrogen content after pre-treatment contained by coal tar is still very high, may have a negative impact to the overall operation life-span of device.The technical process that hydrofining reactor section adopts gas and liquid flowing to combine with gas-liquid counter current reaction zone is recommended in the inventive method.This hydrofining flow process is similar to two-stage hydrogenation treating processes.On the one hand, and flow district and first remove a part of nitrogen impurity, the ammonia generated then and stream leaves reactor with the gas-liquid separation zone in the middle of adverse current, the restraining effect of ammonia to counter-flow reaction zone can be reduced on the one hand; On the other hand, enter raw material and the hydrogen counter current contact of counter-flow reaction zone, also in time the ammonia generated can be proposed counter-flow reaction zone, thus can react under the condition comparing mitigation.Meanwhile, the lower temperature in counter-flow reaction zone is also conducive to promoting aromatic saturation reaction, and denitrification reaction is generally ring-opening reaction, thus refining reaction temperature is reduced further.That is, when processing same inferior raw material under identical air speed, because two-stage reaction has higher hydrogen dividing potential drop and aromatic saturation reaction faster, using two reaction zones to carry out advanced nitrogen needs lower average reaction temperature by than use reactor.
5, for the extra high coal tar raw material of nitrogen content, except adopting at hydrofining reactor and flowing except the flow process that is combined with adverse current, suitable catalyzer can also be coordinated to carry out hydrofining reaction.As can and flow in reaction zone adopt by chloride process prepare carrier produce Hydrobon catalyst, be characterized in that duct is large and concentrated, foreign matter content is low, the effect of carrier and metal is strong, more effectively can reduce the restraining effect of ammonia to catalyzer, especially to processing inferior raw material, there is better activity stability; And the Hydrobon catalyst being prepared carrier production by sulphate method is preferably used in counter-flow reaction zone, be characterized in that duct is relatively little and disperse, the effect of carrier and metal is relatively weak.The catalyst for refining of counter-flow reaction zone has higher activity and better activity stability for the raw material being stripped of most of the nitrogen impurity.Thus the grating of these two kinds of catalyzer can better play the activity of catalyzer.Because hydrofining reaction temperature reduces greatly, thus the running period of device can be improved, or improve the working ability of device under same running period, and catalytic cracking feeds quality can be improved.
Accompanying drawing explanation
Fig. 1 is a kind of principle process flow sheet of the inventive method.
Fig. 2 is the another kind of principle process flow sheet of the inventive method.
Embodiment
The embodiment of this programme is briefly described below in conjunction with device schema.
As shown in Figure 1, the flow process of coal tar multistage hydrogenation treatment technique of the present invention is: after first coal tar raw material 1 mixes with the overhead components of flashing tower 3, enter pretreatment unit 2 and carry out electric desalting operation, remove the metallic impurity such as water, inorganic chlorine ion and sodium, calcium, magnesium, iron contained in coal tar raw material, require de-after stock oil salts contg lower than 3ppm.Material after pretreatment unit desalination enters flashing tower 3, and overhead components loops back pretreatment unit 2, and the tower base stream of flashing tower 3, after filtering, enters ebullated bed preatreating reactors 4, carries out weighted BMO spaces reaction.Boiling bed hydrogenation pretreatment product enters separation and fractionation unit 5, obtains gas, liquid distillate and residue; Wherein residue loops back ebullated bed preatreating reactors 4.Liquid distillate then enters hydrofining reactor 6, and hydrofining reaction effluent enters hydrocracking reactor 7, carries out hydrocracking reaction.Hydrocracking effluent enters separation and fractionation unit 8, and obtain petroleum naphtha 9, diesel oil 10 and unconverted oil (tail oil) 11, wherein unconverted oil 11 returns hydrofining reactor 6.
As shown in Figure 2, the another kind of flow process of the inventive method is: as shown in Figure 2, the flow process of coal tar multistage hydrogenation treatment technique of the present invention is: after first coal tar raw material 1 mixes with the overhead components of flashing tower 3, enter pretreatment unit 2 and carry out electric desalting operation, remove the metallic impurity such as the inorganic chlorine ion that contains in coal tar raw material and sodium, calcium, magnesium, iron, require de-after stock oil salts contg lower than 3ppm.Material after pretreatment unit desalination enters flashing tower 3, and overhead components loops back pretreatment unit 2, and the tower base stream of flashing tower 3, after filtering, enters ebullated bed preatreating reactors 4, carries out weighted BMO spaces reaction.Boiling bed hydrogenation pretreatment product enters separation and fractionation unit 5, obtains gas, liquid distillate and residue; Wherein residue loops back ebullated bed preatreating reactors 4.Liquid distillate then enters hydrofining reactor 6, that hydrofining reactor comprises top and flow reaction zone A, gas-liquid separation zone C and counter-flow reaction zone B.First the liquid distillate that separation and fractionation unit 5 obtain and hydrogen enter and flow reaction zone A, and carry out hydrofining (denitrogenation) reaction, gained effluent enters gas-liquid separation zone C, and gas draws reactor; Liquid enters counter-flow reaction zone B, and the hydrogen counter current contact introduced with reactor lower part, carries out advanced nitrogen reaction; Hydrofining effluent can enter hydrocracking reactor 7 together with hydrogen, carries out hydrocracking reaction.Hydrocracking effluent enters separation and fractionation unit 8, and obtain petroleum naphtha 9, diesel oil 10 and unconverted oil (tail oil) 11, wherein unconverted oil 11 returns hydrofining reactor 6.
For further illustrating all main points of the present invention, enumerate following examples.Wherein, if no special instructions, % is weight percentage.
Wherein boiling bed hydrogenation catalyst is boiling bed hydrogenation special-purpose catalyst, and the character of Hydrobon catalyst lists in table 1, and hydrocracking catalyst is the FC-28 catalyzer of Fushun Petrochemical Research Institute's Development and Production.
The present embodiment is the hydropyrolysis experiment adopting multistage combination process to carry out middle coalite tar distillate.Wherein coal tar raw material character is: density (20 DEG C): 0.9497 g/cm 3, carbon residue: 4.95%; Sulphur: 2277 μ g/g, nitrogen: 3339 μ g/g, saturated point: 22.6%; Fragrance point: 25.5%; Colloid is 51.7%, and bituminous matter is 0.2%; Wherein containing mechanical impurity 1.8%.
Embodiment 1-2
Adopt flow process shown in Fig. 1: the coal tar raw material first in head tank 1 enters electric desalting apparatus and carries out desalination and demetalization, the density that step a) controls the rear raw material of mixing is 0.9 g/cm 3; Rate-determining steps d) final boiling point of product liquid is 510 DEG C.
After hydrocracking, product shunting obtains liquefied gas, petroleum naphtha (C 5-175 DEG C) and clean diesel (175 ~ 360 DEG C), Fractionator Bottom >360 DEG C tail oil all loops back fixed bed hydrogenation refining reaction device.Use Hydrobon catalyst B in embodiment 1, in embodiment 2, use Hydrobon catalyst A.Reaction conditions and test-results list in table 2 and table 3 respectively.
Embodiment 3
Adopt technical process shown in Fig. 2: hydrofining reactor comprises and flows reaction zone and counter-flow reaction zone, and flowing reaction zone and Hydrobon catalyst B is all loaded in counter-flow reaction zone, boiling bed hydrogenation reactor and hydrocracking reactor institute loading catalyst are with embodiment 1-2.Controlling and flowing reaction zone denitrification percent is 75%, and reaction conditions and test-results list in table 2 respectively, table 2-continues and table 4.
Embodiment 4
Adopt technical process shown in Fig. 2: hydrofining reactor comprises and flows reaction zone and counter-flow reaction zone, and flow reaction zone filling Hydrobon catalyst A, counter-flow reaction zone filling Hydrobon catalyst B, boiling bed hydrogenation reactor and hydrocracking reactor institute loading catalyst are with embodiment 1 and 2.Controlling and flowing reaction zone denitrification percent is 75%, and reaction conditions and test-results list in table 2 respectively, table 2-continues and table 4.
Table 1 catalyst property.
Table 2 processing condition (running 500h).
Table 2-continues fixed bed hydrogenation process for refining condition (running 5000h).
* corresponding respectively and flow the temperature of reaction zone and counter-flow reaction zone.
Table 3 product property.
Table 4 product property

Claims (16)

1. a coal tar multistage hydrogenation treatment technique, comprises following content:
A) overhead components that coal tar raw material and step b) obtain is mixed, and go to enter electric desalting unit after heat exchange, carry out electric desalting operation;
B) logistics after step a) desalination enters flash distillation separation column, and isolated overhead components directly returns step a) without cooling, and mixes with coal tar raw material;
C), after logistics out at the bottom of step b) flash distillation separation column tower mixes with hydrogen, after process furnace heating, enter boiling bed hydrogenation reactor, carry out weighted BMO spaces reaction;
D) reaction effluent that step c) obtains enters separator and carries out gas-liquid separation and fractionation, obtains hydrogen-rich gas, carburet hydrogen, product liquid and residue;
E) after step d) gained product liquid mixes with hydrogen, enter hydrofining reactor and carry out hydrofining reaction, the hydrogen-rich gas that step d) obtains uses through purifying treatment Posterior circle;
F) step e) obtains reaction effluent and enters hydrocracking reactor, under hydrocracking catalyst and hydrogen exist, carry out hydrocracking reaction;
G) step f) obtains reaction effluent and is separated, and liquid obtains petroleum naphtha component, diesel component and unconverted oil through fractionation.
2. in accordance with the method for claim 1, it is characterized in that, also comprise step h): the unconverted oil that step g) obtains returns step c), enters hydrofining reactor after mixing with logistics out at the bottom of flash distillation separation column tower.
3. according to technique according to claim 1, it is characterized in that, the coal tar described in step a) is middle coalite tar, the nitrogen content of middle coalite tar is 1500 more than μ g/g, initial boiling point is generally 220 ~ 450 DEG C, and be preferably 300 ~ 420 DEG C, final boiling point is generally 500 ~ 550 DEG C.
4. in accordance with the method for claim 1, it is characterized in that, control in step a) overhead components that coal tar raw material and step b) obtain mixed 20 DEG C density stabilized at 0.800 ~ 0.960g/cm 3.
5. in accordance with the method for claim 1, it is characterized in that, in step b), after the logistics after step a) desalination is first filtered, then enter flash distillation separation column.
6. according to the method described in claim 1 or 5, it is characterized in that, in described step c), step b) flash distillation separation column obtains tower base stream and entering boiling bed hydrogenation reactor again after strainer.
7. in accordance with the method for claim 1, it is characterized in that, the processing condition of the boiling bed hydrogenation reactor described in step c) are: reaction pressure 12 ~ 20MPa, average reaction temperature: 380 ~ 400 DEG C, hydrogen to oil volume ratio 500 ~ 1000, fresh feed volume space velocity is 0.1 ~ 10.0h -1.
8. in accordance with the method for claim 1, it is characterized in that, the endpoint control of step d) gained product liquid 450 ~ 550 DEG C.
9. in accordance with the method for claim 1, it is characterized in that, in step d), obtain the boiling bed hydrogenation reactor that residue loops back step c).
10. in accordance with the method for claim 1, it is characterized in that, in the hydrofining reactor described in step e), stock oil and hydrogen stream passes downwardly through Hydrobon catalyst bed.
11. in accordance with the method for claim 1, it is characterized in that, hydrofining reactor described in step e) comprises the gas and liquid flowing reaction zone on top and the gas-liquid counter current reaction zone of bottom, first the product liquid that step d) obtains enters with hydrogen and flows reaction zone, and flows reaction zone use Hydrobon catalyst; And flow reaction effluent and enter middle gas-liquid separation zone and be separated, gas draws reactor; Liquid then enters the counter-flow reaction zone of bottom, and the hydrogen introduced with reactor bottom carries out counter current contact reaction.
12. according to the method described in claim 10 or 11, it is characterized in that, hydrofining reactor filling Hydrobon catalyst described in step e), described Hydrobon catalyst is made up of carrier and the hydrogenation metal component be loaded on carrier, catalyzer to comprise in the periodic table of elements group VIB active metal component in metal oxide weight 8% ~ 35%, and the VIIIth race's active metal component is in metal oxide weight 1% ~ 7%; Carrier is inorganic refractory oxide.
13. in accordance with the method for claim 11, it is characterized in that, and flowing the catalyzer using in reaction zone and there is following character: the average pore diameter of catalyzer is 7.5 ~ 9.5nm, the volume fraction that the pore volume in the hole of bore dia 4 ~ 10nm accounts for total pore volume is that the pore volume in 70% ~ 90%, <4nm hole accounts for less than 5% of total pore volume; The catalyzer of following character is used: the average pore diameter of catalyzer is 4 to being less than 7.5nm in counter-flow reaction zone, the pore volume in its median pore diameter to be volume fraction that the pore volume in the hole of 4 ~ 10nm accounts for total pore volume be hole of 50 ~ 75%, <4nm accounts for the volume fraction of total pore volume lower than 10%; Wherein with and flow compared with the catalyzer in reaction zone, the average pore diameter of counter-flow reaction zone Hydrobon catalyst used wants the hole of little 0.5 ~ 3nm, aperture 4 ~ 10nm to account for little 10 ~ 30 percentage ratios of volume fraction of total pore volume.
14. in accordance with the method for claim 11, it is characterized in that, in step e) and the denitrification percent flowing reaction zone control as 20wt% ~ 90wt%.
15. in accordance with the method for claim 14, it is characterized in that, the described and processing condition flowing reaction zone are: average reaction temperature is 250 ~ 500 DEG C, is preferably 300 ~ 440 DEG C; Reaction pressure is 5.0 ~ 20.0MPa, is preferably 8.0 ~ 17.0MPa; Hydrogen to oil volume ratio is 100:1 ~ 4000:1, is preferably 400:1 ~ 2000:1; During liquid, volume space velocity is 1.0 ~ 10.0h -1; The processing condition of counter-flow reaction zone are: average reaction temperature is 250 ~ 500 DEG C, and reaction pressure is 5.0 ~ 20.0MPa, and hydrogen to oil volume ratio is 100:1 ~ 2000:1, and during liquid, volume space velocity is 1.0 ~ 10.0h -1.
16. in accordance with the method for claim 1, it is characterized in that, the reaction conditions of the fixed bed hydrogenation cracking reaction described in step f) is: reaction pressure is 12 ~ 20MPa, and average reaction temperature is 380 ~ 430 DEG C, hydrogen to oil volume ratio is 800 ~ 1500, and volume space velocity is 0.1 ~ 5.0h -1.
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CN114433118A (en) * 2020-10-30 2022-05-06 中国科学院宁波材料技术与工程研究所 Fluidized bed hydrogenation catalyst and processing method of coal tar whole fraction

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CN106281407A (en) * 2015-06-24 2017-01-04 中国石油化工股份有限公司 The preprocess method of a kind of coal tar and the production method of fuel oil
CN106281407B (en) * 2015-06-24 2019-02-01 中国石油化工股份有限公司 A kind of preprocess method of coal tar and the production method of fuel oil
CN106854474A (en) * 2016-12-30 2017-06-16 山东胜星化工有限公司 A kind of new coal tar hydrogenating cracker and preparation method thereof
KR20190129685A (en) * 2018-05-11 2019-11-20 이너 몽골리아 성위엔 테크놀로지 컴퍼니 리미티드 Hydrogenated combination process of high quality fuel production by medium and low temperature coal tar
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CN111849552B (en) * 2019-04-30 2021-12-17 中国石油化工股份有限公司 Coal tar full-fraction hydrogenation upgrading method and system
CN114433118A (en) * 2020-10-30 2022-05-06 中国科学院宁波材料技术与工程研究所 Fluidized bed hydrogenation catalyst and processing method of coal tar whole fraction
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