CN104449837B - A kind of full fraction of coal tar hydrogenation dual treatment method - Google Patents
A kind of full fraction of coal tar hydrogenation dual treatment method Download PDFInfo
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- CN104449837B CN104449837B CN201410652462.1A CN201410652462A CN104449837B CN 104449837 B CN104449837 B CN 104449837B CN 201410652462 A CN201410652462 A CN 201410652462A CN 104449837 B CN104449837 B CN 104449837B
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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
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
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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
- C10G2400/02—Gasoline
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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 provides a kind of full fraction of coal tar hydrogenation dual treatment method, by first separating of oil for the coal tar raw material heavy ends obtained being carried out hydrocracking in the first fixed-bed reactor, oil circulation the getting back in the first fixed-bed reactor of low point of the part utilizing hydrofining to produce afterwards carries out cracking reaction together with heavy ends, remain after low point of oil carries out hydro-upgrading in the 3rd fixed-bed reactor, be separated and obtain gasoline, diesel product; Hydrocracking is carried out together with also utilize the low point of oil produced after refining to mix with heavy ends by adopting the mode of step charging, along separate routes hydrogenation after, contribute to promoting hydrogenation efficiency, and the generation of energy slagging prevention, thus the method for the invention adopts fixed-bed reactor just can realize the hydrogenation dual treatment to full fraction of coal tar, the stability obtaining product oil is better, the yield of effective raising acquisition gasoline, diesel oil and quality.
Description
Technical field
The present invention relates to a kind of full fraction of coal tar hydrogenation dual treatment method, belong to the technical field of coal tar hydrogenating process.
Background technology
Along with social economy is lasting, high speed development, the demand of China to petroleum products also increases day by day.But oil belongs to Nonrenewable energy resources, be faced with increasingly exhausted crisis.By contrast, Chinese coal reserves are abundanter, therefore, become a basic orientation of coal processing and utilization by coal preparing liquid fuel.
On the other hand, along with quick growth that is international, domestic steel industry, coking industry presents the trend of high growth, and the output of coal tar is increasing, and the clean processing of coal tar and effective utilization also become more and more important.At present, distill through pre-treatment the various cuts cut in diversity during conventional working method, then process extraction straight product is carried out to methods such as various cut acid-alkali washing, distillation, polymerization, crystallizations; Also some coal tar is directly burnt as low-quality fuel oil after acid-alkali refining, or as emulsion fuel burns after direct emulsification.In coal tar, institute's impurity such as sulfur-bearing, nitrogen becomes sulphur and nitrogen oxide in combustion and discharges into the atmosphere and cause topsoil.And large amount of sewage in acid-alkali refining process, can be produced, can serious environment pollution.Therefore, no matter from the viewpoint of the angle of environment protection or utilize from environment comprehensive, all wish to find an effective chemical process approach, make coal tar obtain upgrading, to expand himself utility value.How effectively to utilize tar resource and make it meet research direction that environmental protection requirement is various countries always.
At present, coal tar hydrogenating technology can be summarized as according to its technical characterstic: coal tar hydrorefining/hydrotreating techniques, delayed coking-hydrocracking process integration technology, the fixed bed hydrogenation cracking technology of coal tar and the suspension bed/slurry bed system/boiling bed hydrogenation cracking technology of coal tar.But, take fixed bed as the hydrogen addition technology of main reactor, because coal tar utilization ratio is low, and colloid in coal tar and heteroatoms are easily in catalyst surface coking, causing the activity of catalyzer and work-ing life to be reduced, therefore, take fixed bed as the hydrogen addition technology of main reactor, only for be with the benzoline (< 370 DEG C) in coal tar for raw material, obtain petroleum naphtha and solar oil product by hydrogenation.
Chinese patent literature CN102796559A discloses a kind of method that oil fuel is produced in hydrocracking, comprise the steps: that (1) stock oil distills, be adopted by stock oil the method for distillation to be separated, obtain the two or more cuts comprising heavy oil fraction; (2) oil-catalyst slurry preparation a part for heavy oil fraction, the hydrogenation heavy distillate being stripped of catalyzer, hydrofining tail oil fraction, catalyzer and vulcanizing agent is mixed together evenly to make oil-catalyst slurry; (3) hydrocracking is carrying out hydrocracking reaction as raw material and oil-catalyst slurry at suspension bed or slurry bed system or bubbling bed hydrogenator using except the part be separated for the preparation of the residual gravity oil distillate except oil-catalyst slurry, isocrackate in the bottom effluent oil obtained; (4) isocrackate is separated, and is be separated by isocrackate, and obtain the fuel-displaced and bottom effluent oil of overhead stream, bottom this, effluent oil contains catalyzer; (5) catalyst separating, is that above-mentioned part bottom effluent oil is carried out solid-liquid separation, obtains catalyst residue and hydrogenation heavy distillate; (6) hydrofining, be stock oil is distilled other cuts of obtaining except heavy oil fraction and above-mentioned overhead stream fuel-displaced as raw material, carry out hydrofining reaction after mixed hydrogen; (7) product fractionation, is that the reactant obtained by hydrofining reaction carries out distillation fractionation, obtains fuel oil fraction and tail oil fraction.In aforesaid method, by distillation being obtained heavy oil fraction, catalyst mix slurry oil carries out hydrocracking reaction at suspension bed or slurry bed system or bubbling bed reactor, avoid the problem easily producing coking when adopting fixed-bed reactor to carry out hydrocracking heavy oil reaction to a certain extent, but, above-mentioned employing suspension bed or bubbling bed or slurry bed system are, after main reactor carries out hydrocracking reaction, obtain the less stable of product oil.In addition, because the manufacture difficulty of suspension bed or bubbling bed or paste state bed reactor is large, involve great expense, operation running cost is high, is unsuitable for large-scale promotion application.
Summary of the invention
Technical problem to be solved by this invention is to adopt suspension bed or bubbling bed or slurry bed system to be after main reactor carries out hydrocracking reaction in prior art, obtain the less stable of product oil, thus a kind of fixed bed that adopts of proposition carries out full fraction of coal tar hydrogenation dual treatment method.
For solving the problems of the technologies described above, technical scheme provided by the invention is as follows:
A kind of full fraction of coal tar hydrogenation dual treatment method, it comprises the steps:
(1) fractionation separates is carried out to coal tar raw material oil, obtain lightweight, middle matter, heavy three kinds of cuts;
(2) mixed with hydrogen by the heavy ends that step (1) obtains, in the first fixed-bed reactor, under hydrocracking catalyst condition, carry out one-level hydrocracking reaction, crackate is separated into cracking light oil and pressure fuel;
(3) the described cracking light oil that step (2) obtains is mixed with step (1) described light ends, middle matter cut, in the second fixed-bed reactor, under Hydrobon catalyst condition, carry out hydrofining reaction, reaction product is separated into rich hydrogen high score gas and low point of oil;
(4) described for step (3) low point of oily part is circulated back to the first fixed-bed reactor in step (2), together with after described low point of oil mixes according to mass ratio 1:2-5:1 with heavy ends, carries out cracking reaction;
By described low point of oily remainder in the 3rd fixed-bed reactor, carry out hydro-upgrading reaction under catalyst for hydro-upgrading condition, reaction product is separated and obtains gasoline, diesel oil and tail oil.
In step (2), before one-level hydrocracking reaction, by described heavy ends in the 4th fixed-bed reactor, carry out protective reaction under hydrogenation protecting catalyst condition.
The temperature of described protective reaction is 220-280 DEG C, and pressure is 15-18MPa, and hydrogen-oil ratio is 800-1500.
Heavy ends after protective reaction is carried out online deslagging process.
In step (3), after described cracking light oil mixes with light ends, middle matter cut, first in the 5th fixed-bed reactor, under hydrogenation protecting catalyst condition, carry out hydrogenation presaturation reaction.
The temperature of described hydrogenation presaturation reaction is 260-320 DEG C, and pressure is 15-18MPa, and hydrogen-oil ratio is 800-1200.
The pressure fuel that step (2) obtains mixes with hydrogen; in the 6th fixed-bed reactor, under hydrocracking catalyst condition, carry out secondary hydrogenation cracking reaction, together with secondary cracked reaction product and the heavy ends after protective reaction mix also, carry out online deslagging process.
Step (4) described tail oil is circulated back to described 6th fixed-bed reactor and carries out secondary hydrogenation cracking reaction.
In step (1), before fractionation is carried out to coal tar raw material oil, also coal tar raw material oil is dewatered and the pre-treatment of de-solid impurity;
Described dehydration pretreatment process comprises the combination of one or more in heating standing evaporation, ultracentrifuge evaporation, batch still evaporation or tube furnace evaporation;
The pretreatment process of described de-solid impurity comprises the combination of one or more in solvent extraction, settleability whizzer or super three phase centrifugation method.
The temperature of described one-level hydrocracking reaction is 380-420 DEG C, and pressure is 15-18MPa, and hydrogen-oil ratio is 800-1500; The temperature of described hydrofining reaction is 340-390 DEG C; The temperature of described hydro-upgrading reaction is 360-400 DEG C, and pressure is 15-18MPa, and hydrogen-oil ratio is 800-1500; The temperature of described secondary hydrogenation cracking reaction is 360-400 DEG C, and pressure is 15-18MPa, and hydrogen-oil ratio is 800-1500.
Technique scheme of the present invention has the following advantages compared to existing technology:
(1) full fraction of coal tar hydrogenation dual treatment method of the present invention, by first separating of oil for the coal tar raw material heavy ends obtained being carried out hydrocracking in the first fixed-bed reactor, the cracking light oil again hydrocracking produced and the separating of oil light ends obtained of described coal tar raw material, in the second fixed-bed reactor, hydrofining is carried out after middle matter cut mixing, oil circulation the getting back in the first fixed-bed reactor of low point of the part utilizing hydrofining to produce afterwards carries out cracking reaction together with heavy ends, remain after low point of oil carries out hydro-upgrading in the 3rd fixed-bed reactor, separation obtains gasoline, diesel product, thus the inventive method is by adopting step charging, hydrocracking is carried out together with after the mode of hydrogenation also utilizes the refining rear low point of oil produced to mix with heavy ends along separate routes, can the generation of effective slagging prevention, achieve the hydrogenation dual treatment that just can carry out full fraction of coal tar in fixed-bed reactor, easily coking is produced when adopting fixed-bed reactor to carry out hydrocracking heavy oil reaction compared to prior art, and adopt suspension bed or bubbling bed or slurry bed system to be after main reactor carries out hydrocracking reaction, obtain the less stable of product oil, the method of the invention adopts fixed-bed reactor just can realize the hydrogenation dual treatment to full fraction of coal tar, the stability obtaining product oil is better, and by adopting step charging, the mode of hydrogenation along separate routes, effective raising obtains gasoline, the yield of diesel oil and quality.In addition, the manufacturing technology of fixed-bed reactor is ripe, manufacturing cost is lower, and operation running cost is also low, is suitable for large-scale promotion application.
(2) full fraction of coal tar hydrogenation dual treatment method of the present invention, by the heavy ends after protective reaction is carried out online deslagging process, be conducive to the coal dust will carried in protective reaction product, the solid impurity such as coke tar refuse or catalyst fines isolates system, avoid art methods in the process of process heavy ends, the solid impurity itself contained in coal tar, subsequent reactor beds will be caused blocking to occur or forms coking center, bed pressure drop increases, affect the stability of device, thus the method for the invention, can the steady running of effective guarantee subsequent reactor, the long period steady running of implement device.
Accompanying drawing explanation
In order to make content of the present invention be more likely to be clearly understood, below according to a particular embodiment of the invention and by reference to the accompanying drawings, the present invention is further detailed explanation, wherein
Fig. 1 is full fraction of coal tar hydrogenation dual treatment device described in the embodiment of the present invention 1.
In figure, Reference numeral is expressed as: 1-first fixed-bed reactor; 11-first separating unit; 2-second fixed-bed reactor; 21-second separating unit; 3-the 3rd fixed-bed reactor; 31-the 3rd separating unit; 32-oil product separating unit; 4-the 4th fixed-bed reactor; 5-the 5th fixed-bed reactor; 6-the 6th fixed-bed reactor; 7-separation column; The online deslagging unit of 8-.
Embodiment
Embodiment 1
The present embodiment provides a kind of full fraction of coal tar hydrogenation dual treatment device, as shown in Figure 1, connects setting successively along technical process direction:
Separation column 7, top is provided with light ends outlet, and middle part is provided with middle matter fraction outlets, and bottom is provided with heavy ends outlet;
4th fixed-bed reactor 4, the heavy ends outlet of top and described separation column 7 is arranged, and the bottom connection of described 4th fixed-bed reactor 4 arranges online deslagging unit 8;
First fixed-bed reactor 1, top is communicated with described online deslagging unit 8 and arranges, the bottom connection of described first fixed-bed reactor 1 arranges the first separating unit 11, and the top of described first separating unit 11 is provided with the outlet of cracking light oil, and bottom is provided with pressure fuel outlet;
6th fixed-bed reactor 6, top and described pressure fuel outlet are arranged, and the bottom of described 6th fixed-bed reactor 6 is communicated with described online deslagging unit 8 and arranges;
5th fixed-bed reactor 5, top exports with described cracking light oil respectively, the light ends of described separation column 7 exports, middle matter fraction outlets is communicated with and arranges;
Second fixed-bed reactor 2, top is communicated with the bottom of described 5th fixed-bed reactor 5 and arranges, the bottom connection of described second fixed-bed reactor 2 arranges the second separating unit 21, described second separating unit 21 be provided with first low point of oil export and second low point of oil export, described first low point of oil export is communicated with described 4th fixed-bed reactor 4 and arranges;
3rd fixed-bed reactor 3, top is communicated with described second low point of oil export and arranges, and the bottom of described 3rd fixed-bed reactor 3 is communicated with and arranges the 3rd separating unit 31;
Oil product separating unit 32, is communicated with described 3rd separating unit 31 and arranges, and described oil product separating unit 32 is provided with fuel dispensing outlet, diesel oil outlet and tail oil outlet; The outlet of described tail oil is communicated with the top of described 6th fixed-bed reactor 6 and arranges.
Further, provide a kind of full fraction of coal tar hydrogenation dual treatment method, it comprises the steps:
(1) first adopted by coal tar raw material oil the standing evaporation of heating and batch still evaporation to carry out processed, then adopt solvent extraction and settleability whizzer to carry out de-solid impurity process;
(2) coal tar raw material oil step (1) obtained is separated in separation column 7, obtains lightweight, middle matter, heavy three kinds of cuts;
By heavy ends in the 4th fixed-bed reactor 4, carry out protective reaction under hydrogenation protecting catalyst condition, described hydrogenation protecting catalyst is Mo-Ni system high porosity catalyzer, active metallic content about 20%, and the temperature of described protective reaction is 220 DEG C, pressure is 15MPa, and hydrogen-oil ratio is 800;
Heavy ends after protective reaction is carried out online deslagging process;
Heavy ends after online deslagging process, in the first fixed-bed reactor 1, carries out one-level hydrocracking reaction under hydrocracking catalyst condition, and crackate utilizes the first separating unit 11 to be separated into cracking light oil and pressure fuel; Described hydrocracking catalyst is W-Ni system cracking catalyst, active metallic content about 28%, and the temperature of described one-level hydrocracking reaction is 380 DEG C, and pressure is 15MPa, and hydrogen-oil ratio is 800;
Pressure fuel is mixed with hydrogen, in the 6th fixed-bed reactor 6, under hydrocracking catalyst condition, carries out secondary hydrogenation cracking reaction, together with secondary cracked reaction product and the heavy ends after protective reaction mix also, carry out online deslagging process; Described hydrocracking catalyst is W-Mo-Ni system cracking catalyst, active metallic content about 33%, and the temperature of described secondary hydrogenation cracking reaction is 360 DEG C, and pressure is 15MPa, and hydrogen-oil ratio is 800;
(3) the described cracking light oil that step (2) obtains is mixed with step (1) described light ends, middle matter cut, first in the 5th fixed-bed reactor 5, under hydrogenation protecting catalyst condition, carry out hydrogenation presaturation reaction; Again in the second fixed-bed reactor 2, carry out hydrofining reaction under Hydrobon catalyst condition, reaction product is separated into rich hydrogen high score gas and low point of oil through the second separating unit 21;
Described hydrogenation protecting catalyst is Mo-Ni system protective material, active metallic content about 22%, and the temperature of described hydrogenation presaturation reaction is 260 DEG C, and pressure is 15MPa, and hydrogen-oil ratio is 800;
Described Hydrobon catalyst is Mo-Ni system finishing agent, active metallic content about 30%, and the temperature of described hydrofining reaction is 340 DEG C, and pressure is 15MPa, and hydrogen-oil ratio is 800;
(4) described for step (3) low point of oily part is circulated back to the first fixed-bed reactor 1 in step (2), together with after described low point of oil mixes according to mass ratio 1:2 with heavy ends, carries out cracking reaction;
By described low point of oily remainder in the 3rd fixed-bed reactor 3, carry out hydro-upgrading reaction under catalyst for hydro-upgrading condition, reaction product is carried out separation obtain gasoline, diesel oil and tail oil through the 3rd separating unit 31, oil product separating unit 32 first;
Described tail oil is circulated back to described 6th fixed-bed reactor 6 and carries out secondary hydrogenation cracking reaction.
Embodiment 2
The present embodiment provides a kind of full fraction of coal tar hydrogenation dual treatment device, connects setting successively along technical process direction:
Separation column 7, top is provided with light ends outlet, and middle part is provided with middle matter fraction outlets, and bottom is provided with heavy ends outlet;
First fixed-bed reactor 1, the heavy ends outlet of top and described separation column 7 is arranged, the bottom connection of described first fixed-bed reactor 1 arranges the first separating unit 11, and the top of described first separating unit 11 is provided with the outlet of cracking light oil, and bottom is provided with pressure fuel outlet;
Second fixed-bed reactor 2, top and described cracking light oil outlet are arranged, the bottom connection of described second fixed-bed reactor 2 arranges the second separating unit 21, described second separating unit 21 be provided with first low point of oil export and second low point of oil export, described first low point of oil export is communicated with described first fixed-bed reactor 1 and arranges;
3rd fixed-bed reactor 3, top is communicated with described second low point of oil export and arranges, and the bottom of described 3rd fixed-bed reactor 3 is communicated with and arranges described oil product separating unit 32, and described oil product separating unit 32 is provided with fuel dispensing outlet, diesel oil outlet and tail oil outlet.
Further, provide a kind of full fraction of coal tar hydrogenation dual treatment method, it comprises the steps:
(1) adopt separation column 7 to be separated coal tar raw material oil, obtain lightweight, middle matter, heavy three kinds of cuts;
(2) mixed with hydrogen by the heavy ends that step (1) obtains, in the first fixed-bed reactor 1, carry out one-level hydrocracking reaction under hydrocracking catalyst condition, crackate is separated into cracking light oil and pressure fuel;
Described hydrocracking catalyst is W-Ni system cracking catalyst, active metallic content about 28%, and the temperature of described one-level hydrocracking reaction is 420 DEG C, and pressure is 18MPa, and hydrogen-oil ratio is 1500;
(3) the described cracking light oil that step (2) obtains is mixed with step (1) described light ends, middle matter cut, in the second fixed-bed reactor 2, carry out hydrofining reaction under Hydrobon catalyst condition, reaction product is separated into rich hydrogen high score gas and low point of oil;
Described Hydrobon catalyst is Mo-Ni system finishing agent, active metallic content about 30%, and the temperature of described hydrofining reaction is 390 DEG C, and pressure is 18MPa, and hydrogen-oil ratio is 1500;
(4) described for step (3) low point of oily part is circulated back to the first fixed-bed reactor 1 in step (2), together with after described low point of oil mixes according to mass ratio 5:1 with heavy ends, carries out cracking reaction;
By described low point of oily remainder in the 3rd fixed-bed reactor 3, carry out hydro-upgrading reaction under catalyst for hydro-upgrading condition, reaction product is separated and obtains gasoline, diesel oil and tail oil.
Embodiment 3
The present embodiment provides a kind of full fraction of coal tar hydrogenation dual treatment device, connects setting successively along technical process direction:
Separation column 7, top is provided with light ends outlet, and middle part is provided with middle matter fraction outlets, and bottom is provided with heavy ends outlet;
4th fixed-bed reactor 4, the heavy ends outlet of top and described separation column 7 is arranged, and the bottom connection of described 4th fixed-bed reactor 4 arranges online deslagging unit 8;
First fixed-bed reactor 1, top is communicated with described online deslagging unit 8 and arranges, the bottom connection of described first fixed-bed reactor 1 arranges the first separating unit 11, and the top of described first separating unit 11 is provided with the outlet of cracking light oil, and bottom is provided with pressure fuel outlet;
6th fixed-bed reactor 6, top and described pressure fuel outlet are arranged, and the bottom of described 6th fixed-bed reactor 6 is communicated with described online deslagging unit 8 and arranges;
5th fixed-bed reactor 5, top exports with described cracking light oil respectively, the light ends of described separation column 7 exports, middle matter fraction outlets is communicated with and arranges;
Second fixed-bed reactor 2, top is communicated with the bottom of described 5th fixed-bed reactor 5 and arranges, the bottom connection of described second fixed-bed reactor 2 arranges the second separating unit 21, described second separating unit 21 be provided with first low point of oil export and second low point of oil export, described first low point of oil export is communicated with described 4th fixed-bed reactor 4 and arranges;
3rd fixed-bed reactor 3, top is communicated with described second low point of oil export and arranges, and the bottom of described 3rd fixed-bed reactor 3 is communicated with and arranges the 3rd separating unit 31;
Oil product separating unit 32, is communicated with described 3rd separating unit 31 and arranges, and described oil product separating unit 32 is provided with fuel dispensing outlet, diesel oil outlet and tail oil outlet; The outlet of described tail oil is communicated with the top of described 6th fixed-bed reactor 6 and arranges.
Further, provide a kind of full fraction of coal tar hydrogenation dual treatment method, it comprises the steps:
(1) first adopted by coal tar raw material oil the standing evaporation of heating and batch still evaporation to carry out processed, then adopt solvent extraction and settleability whizzer to carry out de-solid impurity process;
(2) coal tar raw material oil step (1) obtained is separated in separation column 7, obtains lightweight, middle matter, heavy three kinds of cuts;
Heavy ends is in the 4th fixed-bed reactor 4, carry out protective reaction under hydrogenation protecting catalyst condition, described hydrogenation protecting catalyst is Mo-Ni system high porosity catalyzer, active metallic content about 20%, and the temperature of described protective reaction is 280 DEG C, pressure is 18MPa, and hydrogen-oil ratio is 1500;
Heavy ends after protective reaction is carried out online deslagging process;
Heavy ends after online deslagging process process mixes with hydrogen, in the first fixed-bed reactor 1, carries out one-level hydrocracking reaction under hydrocracking catalyst condition, and crackate utilizes the first separating unit 11 to be separated into cracking light oil and pressure fuel; Described hydrocracking catalyst is W-Ni system cracking catalyst, active metallic content about 28%, and the temperature of described one-level hydrocracking reaction is 400 DEG C, and pressure is 18MPa, and hydrogen-oil ratio is 1500;
Pressure fuel is mixed with hydrogen, in the 6th fixed-bed reactor 6, under hydrocracking catalyst condition, carries out secondary hydrogenation cracking reaction, together with secondary cracked reaction product and the heavy ends after protective reaction mix also, carry out online deslagging process; Described hydrocracking catalyst is W-Mo-Ni system cracking catalyst, active metallic content about 33%, and the temperature of described secondary hydrogenation cracking reaction is 400 DEG C, and pressure is 18MPa, and hydrogen-oil ratio is 1500;
(3) the described cracking light oil that step (2) obtains is mixed with step (1) described light ends, middle matter cut, first in the 5th fixed-bed reactor 5, under hydrogenation protecting catalyst condition, carry out hydrogenation presaturation reaction; Again in the second fixed-bed reactor 2, carry out hydrofining reaction under Hydrobon catalyst condition, reaction product is separated into rich hydrogen high score gas and low point of oil through the second separating unit 21;
Described hydrogenation protecting catalyst is Mo-Ni system protective material, active metallic content about 22%, and the temperature of described hydrogenation presaturation reaction is 320 DEG C, and pressure is 18MPa, and hydrogen-oil ratio is 1500;
Described Hydrobon catalyst is Mo-Ni system finishing agent, active metallic content about 30%, and the temperature of described hydrofining reaction is 340 DEG C, and pressure is 18MPa, and hydrogen-oil ratio is 1500;
(4) described for step (3) low point of oily part is circulated back to the first fixed-bed reactor 1 in step (2), together with after described low point of oil mixes according to mass ratio 1:1 with heavy ends, carries out cracking reaction;
By described low point of oily remainder in the 3rd fixed-bed reactor 3, carry out hydro-upgrading reaction under catalyst for hydro-upgrading condition, reaction product is carried out separation obtain gasoline, diesel oil and tail oil through the 3rd separating unit 31, oil product separating unit 32 first;
Described tail oil is circulated back to described 6th fixed-bed reactor 6 and carries out secondary hydrogenation cracking reaction.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (10)
1. a full fraction of coal tar hydrogenation dual treatment method, it comprises the steps:
(1) fractionation separates is carried out to coal tar raw material oil, obtain lightweight, middle matter, heavy three kinds of cuts;
(2) mixed with hydrogen by the heavy ends that step (1) obtains, in the first fixed-bed reactor, under hydrocracking catalyst condition, carry out one-level hydrocracking reaction, crackate is separated into cracking light oil and pressure fuel;
(3) the described cracking light oil that step (2) obtains is mixed with step (1) described light ends, middle matter cut, in the second fixed-bed reactor, under Hydrobon catalyst condition, carry out hydrofining reaction, reaction product is separated into rich hydrogen high score gas and low point of oil;
(4) described for step (3) low point of oily part is circulated back to the first fixed-bed reactor in step (2), together with after described low point of oil mixes according to mass ratio 1:2-5:1 with heavy ends, carries out cracking reaction;
By described low point of oily remainder in the 3rd fixed-bed reactor, carry out hydro-upgrading reaction under catalyst for hydro-upgrading condition, reaction product is separated and obtains gasoline, diesel oil and tail oil.
2. full fraction of coal tar hydrogenation dual treatment method according to claim 1; it is characterized in that; in step (2), before one-level hydrocracking reaction, by described heavy ends in the 4th fixed-bed reactor, carry out protective reaction under hydrogenation protecting catalyst condition.
3. full fraction of coal tar hydrogenation dual treatment method according to claim 2, is characterized in that, the temperature of described protective reaction is 220-280 DEG C, and pressure is 15-18MPa, and hydrogen-oil ratio is 800-1500.
4. the full fraction of coal tar hydrogenation dual treatment method according to Claims 2 or 3, is characterized in that, the heavy ends after protective reaction is carried out online deslagging process.
5. full fraction of coal tar hydrogenation dual treatment method according to claim 4; it is characterized in that; in step (3), after described cracking light oil mixes with light ends, middle matter cut, first in the 5th fixed-bed reactor, under hydrogenation protecting catalyst condition, carry out hydrogenation presaturation reaction.
6. full fraction of coal tar hydrogenation dual treatment method according to claim 5, is characterized in that, the temperature of described hydrogenation presaturation reaction is 260-320 DEG C, and pressure is 15-18MPa, and hydrogen-oil ratio is 800-1200.
7. full fraction of coal tar hydrogenation dual treatment method according to claim 4; it is characterized in that; the pressure fuel that step (2) obtains mixes with hydrogen; in the 6th fixed-bed reactor, under hydrocracking catalyst condition, carry out secondary hydrogenation cracking reaction, together with secondary cracked reaction product and the heavy ends after protective reaction mix also, carry out online deslagging process.
8. the full fraction of coal tar hydrogenation dual treatment method according to claim 1 or 2 or 3 or 5 or 6 or 7, is characterized in that, step (4) described tail oil is circulated back to described 6th fixed-bed reactor and carries out secondary hydrogenation cracking reaction.
9. full fraction of coal tar hydrogenation dual treatment method according to claim 8, is characterized in that, in step (1), before carrying out fractionation to coal tar raw material oil, also dewaters and the pre-treatment of de-solid impurity to coal tar raw material oil;
Described dehydration pretreatment process comprises the combination of one or more in heating standing evaporation, ultracentrifuge evaporation, batch still evaporation or tube furnace evaporation;
The pretreatment process of described de-solid impurity comprises the combination of one or more in solvent extraction, settleability whizzer or super three phase centrifugation method.
10. the full fraction of coal tar hydrogenation dual treatment method according to claim 1 or 2 or 3 or 5 or 6 or 7 or 9, it is characterized in that, the temperature of described one-level hydrocracking reaction is 380-420 DEG C, and pressure is 15-18MPa, and hydrogen-oil ratio is 800-1500; The temperature of described hydrofining reaction is 340-390 DEG C; The temperature of described hydro-upgrading reaction is 360-400 DEG C, and pressure is 15-18MPa, and hydrogen-oil ratio is 800-1500; The temperature of described secondary hydrogenation cracking reaction is 360-400 DEG C, and pressure is 15-18MPa, and hydrogen-oil ratio is 800-1500.
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| CN101885982A (en) * | 2010-06-23 | 2010-11-17 | 煤炭科学研究总院 | Hydrogenation method for coal tar suspension bed of heterogeneous catalyst |
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| CN101885982A (en) * | 2010-06-23 | 2010-11-17 | 煤炭科学研究总院 | Hydrogenation method for coal tar suspension bed of heterogeneous catalyst |
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