CN104650973A - Hydrogenation process for coal tar through two-stage method - Google Patents
Hydrogenation process for coal tar through two-stage method Download PDFInfo
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- CN104650973A CN104650973A CN201510080037.4A CN201510080037A CN104650973A CN 104650973 A CN104650973 A CN 104650973A CN 201510080037 A CN201510080037 A CN 201510080037A CN 104650973 A CN104650973 A CN 104650973A
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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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/307—Cetane number, cetane index
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Abstract
The invention discloses a hydrogenation process for coal tar through a two-stage method. The method comprises the following steps: performing a first-step hydrofining reaction on the coal tar at a high temperature of 360-400 DEG C to obtain a first-step hydrofining reaction product, reducing the temperature to 300-350 DEG C through a heat exchange cooling device, and performing a second-step hydrofining reaction. The method is capable of promoting the better forward operation of the hydrofining reaction, increasing the hydrogenation saturation of the aromatic hydrocarbon in the coal tar and perfectly solving the problems of high aromatic hydrocarbon content, low cetane number and bad oxidation stability in the product oil prepared from the current coal tar hydrogenation process. By adopting the hydrogenation process for coal tar through a two-stage method, the aromatic hydrocarbon content in the product oil can be effectively reduced, the cetane number and the oxidation stability of the product oil are increased and the quality of the product oil is improved.
Description
Technical field
The present invention relates to a kind of two-stage method coal tar hydrogenation process, belong to the technical field of coal tar hydrogenating.
Background technology
Along with the growth at full speed of China's economy, the continuous increase of liquid fuel oil demand and the petroleum resources contradiction day by day between exhaustion is further obvious.Under this energy situation, for obtaining new alternate resources, ensure national energy security, rely on China compared with the coal resources of horn of plenty and numerous coal chemical enterprises, technology as the producing clean fuel oil by hydrogenation of coal tar product of pyrolysis byproducts obtains to be promoted rapidly, thus the clean processing of coal tar and effective utilization also become more and more important.
Coal tar hydrogenating technology refers to that coal tar is under hydro condition, with catalyst exposure, series of chemical occurs, removes sulphur in coal tar, nitrogen, oxygen and metal impurities, reduce molecular weight, improve oil quality, obtain the technology of qualified clean fuel oil product.Due to the complicacy of coal tar composition, cause the complicacy of hydrogenation process, therefore, in order to adapt to various raw material, solving different engineering problems, defining many coal tar hydrogenation process differed from one another, comprise the adjustment of technique and the improvement of catalyzer.
Chinese patent literature CN102041087A discloses a kind of method for hydrogen cracking of deep drawing anthracene oil, specifically comprise the steps: (1) in presence of hydrogen, deep drawing anthracene oil enters hydrofining reaction district, contacts successively carry out hydrofining reaction with hydrogenation protecting catalyst with Hydrobon catalyst; (2) the generation oil of step (1) hydrofining gained carries out gas-liquid separation through high pressure hot separator; (3) liquid product that step (2) high pressure hot separator separates enters thermal low-pressure separators and carries out further gas-liquid separation, and the heat that thermal low-pressure separators separates low point of oil is partly recirculated to hydrofining reaction district; (4) step (3) remainder heat low point of oil enters hydrocracking reaction district, in presence of hydrogen, takes off after Pd/carbon catalyst to contact with hydrocracking catalyst and react successively, obtain isocrackate through Hydrobon catalyst, hydrogenation; (5) step (4) gained isocrackate with enter cold high pressure separator from the isolated gas of high pressure hot separator; (6) liquid that separates of step (5) cold high pressure separator and the isolated gas of thermal low-pressure separators enter cold low separator; (7) the isolated liquid of step (6) cold low separator is after product stripping tower stripping, and stripping tower bottom liquid removes product separation column, obtains gasoline and diesel oil distillate.But in the diesel oil distillate that aforesaid method prepares, aromaticity content is higher, and cetane value is low and oxidation stability is poor.
In addition, in aforesaid method, the catalyst loading order of hydrocracking reaction section is followed successively by Hydrobon catalyst, removal of ccr by hydrotreating catalyzer and hydrocracking catalyst, the unsaturated hydrocarbons that produces in hydrocracking process can be caused like this and react the mercaptan generated further with hydrogen sulfide remaining because there is no the effect of rear catalyst for refining, and then also can cause that the cetane value of product oil is low and oxidation stability is poor.
Summary of the invention
It is higher that technical problem to be solved by this invention is that coal tar hydrogenation process of the prior art prepares heavy constituent content in gasoline and diesel oil distillate, quality product is low, thus propose a kind of can effectively improving product oil yield and the two-stage method coal tar hydrogenation process of quality.
For solving the problems of the technologies described above, technical scheme of the present invention is as follows:
A kind of two-stage method coal tar hydrogenation process, it comprises the steps:
(1) under Hydrobon catalyst exists, coal tar first carries out the first step hydrofining reaction at 360-400 DEG C, obtain the first step hydrofining reaction product and be cooled to 300-350 DEG C through heat exchange refrigerating unit, again second step hydrofining reaction is carried out to the first step hydrofining reaction product after cooling, obtain second step hydrotreated product;
(2) step (1) described second step hydrotreated product is separated through high pressure hot separator and obtains hot high score gas and hot high score oil;
(3) the described hot high score gas of step (2) is separated through cold high pressure separator and obtains cold high score gas and cold high score oil, and the described hot high score oil of step (2) is separated through thermal low-pressure separators and obtains heat low point of gas and heat low point of oil;
(4) part oily for low point of step (3) described heat is returned step (1) and described coal tar mix and together with carry out described the first step hydrofining reaction;
Under hydrocracking catalyst exists, a residue part oily to low point of step (3) described heat carries out hydrocracking reaction, obtains isocrackate;
(5) step (4) described isocrackate is separated through cold high pressure separator and obtains cracking cold high score gas and the cold high score oil of cracking;
(6) be separated through cold low separator together after described to step (5) described cracking cold high score oil and step (3) cold high score oil being mixed and obtain cold low point of oil and cold low point of gas;
(7) described for step (6) cold low point of oil, cold low point of gas and step (3) described heat low point of gas are mixed also input product separating unit together and is separated, obtain gasoline products, diesel product and hydrogenation tail oil.
Described the first step hydrofining reaction carries out at the first hydrofining reaction unit, described second step hydrofining reaction carries out at the second hydrofining reaction unit, described first hydrofining reaction units in series arranges 3-4 hydrofining reactor, and described second hydrofining reaction unit arranges 1 hydrofining reactor.
The pressure of described the first step hydrofining reaction is 14-18MPa, and hydrogen to oil volume ratio is 1000:1-2000:1, and volume space velocity is 0.3-1.5h
-1;
The pressure of second step hydrofining reaction is 14-18MPa, and hydrogen to oil volume ratio is 1000:1-2000:1, and volume space velocity is 0.3-1.5h
-1;
The heap of hydrocracking catalyst described in described first hydrofining reactor is than being 0.7-0.8g/ml, and the heap of hydrocracking catalyst described in described second hydrogenator is than being 0.6-0.7g/ml.
Between described first hydrofining reaction unit and the second hydrofining reaction unit, heat exchange refrigerating unit is set.
In step (1), described Hydrobon catalyst is with one or both in Mo or Ni for active ingredient, take aluminum oxide as carrier; The pore volume 0.20-0.50mL/g of described Hydrobon catalyst, specific surface area 100-200m
2/ g.
In step (4), the heap of described hydrocracking catalyst is than being 0.65-0.85g/ml.
In step (4), the heap of described hydrocracking catalyst is than being 0.65-0.85g/ml.
The pressure of described hydrocracking reaction is temperature is 360-420 DEG C, and pressure is 14-18Mpa, and hydrogen to oil volume ratio is 1500:1-2500:1, and volume space velocity is 0.25-0.75h
-1.
As the recycle hydrogen of hydrocracking in hydrofining in step (1) and step (4) and cold hydrogen together with step (5) described cracking cold high score gas and the described cold high score gas of step (3) being mixed also.
Described hydrocracking reaction is carried out by all or part of input step (4) of step (7) described hydrogenation tail oil.
Technique scheme of the present invention has the following advantages compared to existing technology:
(1) two-stage method coal tar hydrogenation process of the present invention, by first carrying out the first step hydrofining reaction at comparatively high temps 360-400 DEG C to coal tar, obtain the first step hydrofining reaction product and be cooled to 300-350 DEG C through heat exchange refrigerating unit, carry out second step hydrofining reaction again, be conducive to impelling hydrofining reaction better forward carry out, and contribute to the hydrotreated lube base oil improving aromatic hydrocarbons in coal tar, thus better can solving coal tar hydrogenation process of the prior art, to prepare aromaticity content in product oil higher, low and the problem of oxidation stability difference of cetane value, two-stage method coal tar hydrogenation process of the present invention can divide content by the fragrance effectively reduced in product oil, improve cetane value and the oxidation stability of product oil, the quality of product oil is high,
Moreover, technique of the present invention carries out thermal low separation again by described hydrotreated product is separated through thermal high the liquid phase obtained, be conducive to removing further the ammonia nitrogen compounds be dissolved in oil product, the heat low point of oil making to enter cracking zone is more clean, thus ensure that hydrocracking catalyst maintains higher catalytic activity for a long time, the cycle of operation of extension fixture, avoid the easy inactivation of hydrocracking catalyst in prior art, the problem that life cycle is short.
(2) two-stage method coal tar hydrogenation process of the present invention, limit the heap of described hydrocracking catalyst than being 0.65-0.85g/ml, thus by reducing the charge weitght of unit volume hydrocracking catalyst, while reduction catalyzer use cost, the porosity of catalyst reactor is improved, and then be conducive to the open loop saturated reaction of polycyclic aromatic hydrocarbons heavy constituent in coal tar, improve the quality of product oil.
(3) two-stage method coal tar hydrogenation process of the present invention, also isolate described hydrogenation tail oil at product separation oil simultaneously, and select as required to carry out the first step hydrofining reaction by being separated the described hydrogenation tail oil obtained, or described hydrogenation tail oil is carried out described hydrocracking reaction, thus realize product oil distillate accurate cutting, improve product oil quality while, effectively can also improve the hydrogenation efficiency of coal tar, realize rational and efficient use and the energy-saving and emission-reduction of full fraction of coal tar.
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 the schema of two-stage method coal tar hydrogenation process of the present invention.
In figure, Reference numeral is expressed as: 1-coal tar, the new hydrogen of 2-, 3-recycle hydrogen, 4-recycle hydrogen, 5-the first step hydrotreated product, 6-second step hydrotreated product, the hot high score oil of 7-, the hot high score gas of 8-, 9-heat low point of gas, 10-first burst of heat low point of oil, the cold high score gas of 11-, 12-isocrackate, the cold high score oil of 13-, 14-sour water, the cold high score gas of 15-cracking, the cold low point of gas of 16-, 17-sour water, 18-sour water, 19-sour water, 20-second burst of heat low point of oil, the cold high score oil of 21-cracking, 22-gasoline products, 23-diesel product, 24-hydrogenation tail oil, 25-first hydrofining reaction unit, 26-heat exchange refrigerating unit, 27-second hydrofining reaction unit, 28-high pressure hot separator, 29-refines cold high pressure separator, 30-thermal low-pressure separators, 31-hydrocracking reactor, 32-cracking cold high pressure separator, 33-cold low separator, 34-circulating hydrogen compressor, 35-make-up hydrogen compressor, 36-product separation unit, the cold low point of oil of 37-.
Embodiment
Embodiment 1
The present embodiment provides a kind of two-stage method coal tar hydrogenation process, and as shown in Figure 1, concrete steps are as follows:
(1) under Hydrobon catalyst exists, be incorporated in the first hydrofining reaction unit 25 carry out the first step hydrofining reaction by mixed to coal tar 1 and recycle hydrogen 3, obtain hydrotreated product 5;
Described first hydrofining reaction unit 25 comprises three identical first hydrofining reactors be arranged in series, described in each described first hydrofining reactor, the temperature of the first step hydrofining reaction is 380 DEG C, pressure is 16MPa, hydrogen to oil volume ratio is 1500:1, and volume space velocity is 0.5; The heap of hydrocracking catalyst described in described first hydrofining reactor is than being 0.7g/ml;
Described Hydrobon catalyst comprises 17wt% molybdenum oxide, 5wt% nickel oxide, and surplus is silica support or alumina supporter, and the pore volume of described Hydrobon catalyst is 0.4mL/g, and specific surface area is 185m
2/ g,
(2) described for step (1) the first step hydrotreated product 5 is first passed into heat exchange refrigerating unit 26 to carry out heat exchange and be cooled to 330 DEG C; Afterwards under Hydrobon catalyst exists, the first step hydrotreated product 5 after described heat exchange cooling process is carried out second step hydrofining reaction at the second hydrofining reaction unit 27 (arranging 1 the second hydrofining reactor), obtains second step hydrotreated product 6;
The temperature of described second step hydrofining reaction is 380 DEG C, and pressure is 16MPa, and hydrogen to oil volume ratio is 1500:1, and volume space velocity is 0.5; The heap of hydrocracking catalyst described in described second hydrofining reactor is than being 0.6g/ml;
Described Hydrobon catalyst comprises 17wt% molybdenum oxide, 5wt% nickel oxide, and surplus is silica support or alumina supporter, and the pore volume of described Hydrobon catalyst is 0.4mL/g, and specific surface area is 185m
2/ g;
(3) adopted by step (2) described second step hydrotreated product 6 high pressure hot separator 28 to carry out thermal high separation and obtain hot high score gas 8 and hot high score oil 7;
(4) adopted by described for step (3) hot high score gas 8 refining cold high pressure separator 29 to carry out cold anticyclone separation and obtain cold high score gas 11 and cold high score oil 13, and isolate sour water 17, discharge system carries out sewage disposal;
Adopt thermal low-pressure separators 30 to carry out thermal low separation to described hot high score oil 7 and obtain heat low point of gas 9 and heat low point of oil, and isolate sour water 18, discharge system carries out sewage disposal;
(5) using a part oily for low point of step (4) described heat as first burst of heat low point of oil 10 return step (1) and described coal tar 1, recycle hydrogen 3 mix and together with carry out described the first step hydrofining reaction;
Under hydrocracking catalyst exists, in hydrocracking reactor 31, carry out hydrocracking reaction after the recycle hydrogen 4 that the new hydrogen 2 residue oily for low point of step (4) described heat part inputted with make-up hydrogen compressor 35 as second burst of heat low point of oil 20, circulating hydrogen compressor 34 input mixes, obtain isocrackate 12;
Wherein, described hydrocracking catalyst comprises 8wt% nickel oxide, 22wt% Tungsten oxide 99.999, and surplus is silica support or alumina supporter; The heap of described hydrocracking catalyst is than being 0.75g/ml;
Described hydrocracking reaction for temperature be 390 DEG C, pressure is 16Mpa, and hydrogen to oil volume ratio is 2000:1, and volume space velocity is 0.5h
-1;
(6) adopted by step (5) described isocrackate 12 cracking cold high pressure separator 32 to carry out cold anticyclone and be separated into cracking cold high score gas 15 and the cold high score oil 21 of cracking, and isolate sour water 14, discharge system carries out sewage disposal;
(7) in recycle hydrogen and cold hydrogen input step (1), described the first step hydrofining reaction is carried out together with being mixed by described to step (6) described cracking cold high score gas 15 and step (4) cold high score gas 11 also;
Adopt cold low separator 33 to carry out cold low after being mixed with the described cold high score of step (4) oily 13 by step (6) described cracking cold high score oil 21 to be together separated and to obtain cold low point of oil 37 and cold low point of gas 16, and isolate sour water 19, discharge system carries out sewage disposal;
(8) described for step (7) cold low point of oil 37, cold low point of gas 16 and step (4) described heat low point of gas 9 are mixed also input product separating unit 36 together and is separated, obtain gasoline products 22, diesel product 23 and hydrogenation tail oil 24; Described hydrocracking reaction is carried out afterwards by described hydrogenation tail oil 24 input step (5).
Embodiment 2
The present embodiment provides a kind of two-stage method coal tar hydrogenation process, and concrete steps are as follows:
(1) under Hydrobon catalyst exists, be incorporated in the first hydrofining reaction unit 25 carry out the first step hydrofining reaction by mixed to coal tar 1 and recycle hydrogen 3, obtain the first hydrotreated product 5;
Described first hydrofining reaction unit 25 comprises three identical first hydrofining reactors be arranged in series, described in each described first hydrofining reactor, the temperature of the first step hydrofining reaction is 400 DEG C, pressure is 18MPa, hydrogen to oil volume ratio is 2000:1, and volume space velocity is 1.5h
-1; The heap of hydrocracking catalyst described in described first hydrofining reactor is than being 0.8g/ml;
Described Hydrobon catalyst comprises 5wt% molybdenum oxide, 1wt% nickel oxide, and surplus is silica support or alumina supporter, and the pore volume of described Hydrobon catalyst is 0.2mL/g, and specific surface area is 100m
2/ g;
(2) described for step (1) the first hydrotreated product 5 is first passed into heat exchange refrigerating unit 26 to carry out heat exchange and be cooled to 300 DEG C; Afterwards under the second Hydrobon catalyst exists, the first hydrotreated product 5 after described heat exchange cooling process is carried out second step hydrofining reaction at the second hydrofining reaction unit 27 (arranging a reactor), obtains second step hydrotreated product 6;
The temperature of described second step hydrofining reaction is 400 DEG C, and pressure is 18MPa, and hydrogen to oil volume ratio is 2000:1, and volume space velocity is 1.5h
-1; The heap of hydrocracking catalyst described in described second hydrofining reactor is than being 0.7g/ml;
Described Hydrobon catalyst comprises 5wt% molybdenum oxide, 1wt% nickel oxide, and surplus is silica support or alumina supporter, and the pore volume of described Hydrobon catalyst is 0.2mL/g, and specific surface area is 100m
2/ g;
(3) adopted by step (2) described second step hydrotreated product 6 high pressure hot separator 28 to carry out thermal high separation and obtain hot high score gas 8 and hot high score oil 7;
(4) adopted by described for step (3) hot high score gas 8 refining cold high pressure separator 29 to carry out cold anticyclone separation and obtain cold high score gas 11 and cold high score oil 13, and isolate sour water 17, discharge system carries out sewage disposal;
Adopt thermal low-pressure separators 30 to carry out thermal low separation to described hot high score oil 7 and obtain heat low point of gas 9 and heat low point of oil, and isolate sour water 18, discharge system carries out sewage disposal;
(5) using a part oily for low point of step (4) described heat as first burst of heat low point of oil 10 return step (1) and described coal tar 1, recycle hydrogen 3 mix and together with carry out described the first step hydrofining reaction;
Under hydrocracking catalyst exists, in hydrocracking reactor 31, carry out hydrocracking reaction after the recycle hydrogen 4 that the new hydrogen 2 residue oily for low point of step (4) described heat part inputted with make-up hydrogen compressor 35 as second burst of heat low point of oil 20, circulating hydrogen compressor 34 input mixes, obtain isocrackate 12;
Wherein, described hydrocracking catalyst comprises 8wt% nickel oxide, 22wt% Tungsten oxide 99.999, and surplus is silica support or alumina supporter; The heap of described hydrocracking catalyst is than being 0.65g/ml;
The pressure of described hydrocracking reaction is temperature is 420 DEG C, and pressure is 18Mpa, and hydrogen to oil volume ratio is 2500:1, and volume space velocity is 0.75h
-1;
(6) adopted by step (5) described isocrackate 12 cracking cold high pressure separator 32 to carry out cold anticyclone and be separated into cracking cold high score gas 15 and the cold high score oil 21 of cracking, and isolate sour water 14, discharge system carries out sewage disposal;
(7) in recycle hydrogen and cold hydrogen input step (1), described the first step hydrofining reaction is carried out together with being mixed by described to step (6) described cracking cold high score gas 15 and step (4) cold high score gas 11 also;
Adopt cold low separator 33 to carry out cold low after being mixed with the described cold high score of step (4) oily 13 by step (6) described cracking cold high score oil 21 to be together separated and to obtain cold low point of oil 37 and cold low point of gas 16, and isolate sour water 19, discharge system carries out sewage disposal;
(8) described for step (7) cold low point of oil 37, cold low point of gas 16 and step (4) described heat low point of gas 9 are mixed also input product separating unit 36 together and is separated, obtain gasoline products 22, diesel product 23 and hydrogenation tail oil 24; Carry out described hydrocracking reaction by the part input step (5) of described hydrogenation tail oil 24 afterwards, remainder hydrogenation tail oil is arranged outward.
Embodiment 3
The present embodiment provides a kind of two-stage method coal tar hydrogenation process, and concrete steps are as follows:
(1) under Hydrobon catalyst exists, be incorporated in the first hydrofining reaction unit 25 carry out the first step hydrofining reaction by mixed to coal tar 1 and recycle hydrogen 3, obtain the first step hydrotreated product 5;
Described first hydrofining reaction unit 25 comprises three identical first hydrofining reactors be arranged in series, described in each described first hydrofining reactor, the temperature of the first step hydrofining reaction is 360 DEG C, pressure is 16Mpa, hydrogen to oil volume ratio is 1500:1, and volume space velocity is 0.5h
-1; The heap of hydrocracking catalyst described in described first hydrofining reactor is than being 0.75g/ml;
Described Hydrobon catalyst comprises 25wt% molybdenum oxide, 10wt% nickel oxide, and surplus is silica support or alumina supporter, and the pore volume of described Hydrobon catalyst is 0.5mL/g, and specific surface area is 200m
2/ g;
(2) described for step (1) the first hydrotreated product 5 is first passed into heat exchange refrigerating unit 26 to carry out heat exchange and be cooled to 350 DEG C; Afterwards under Hydrobon catalyst exists, the first hydrotreated product 5 after described heat exchange cooling process is carried out second step hydrofining reaction at the second hydrofining reaction unit 27, obtains second step hydrotreated product 6;
The temperature of described second step hydrofining reaction is 360 DEG C, and pressure is 16Mpa, and hydrogen to oil volume ratio is 1500:1, and volume space velocity is 0.5h
-1; The heap of hydrocracking catalyst described in described second hydrofining reactor is than being 0.65g/ml;
Described Hydrobon catalyst comprises 25wt% molybdenum oxide, 10wt% nickel oxide, and surplus is silica support or alumina supporter, and the pore volume of described Hydrobon catalyst is 0.5mL/g, and specific surface area is 200m
2/ g;
(3) adopted by step (2) described second step hydrotreated product 6 high pressure hot separator 28 to carry out thermal high separation and obtain hot high score gas 8 and hot high score oil 7;
(4) adopted by described for step (3) hot high score gas 8 refining cold high pressure separator 29 to carry out cold anticyclone separation and obtain cold high score gas 11 and cold high score oil 13, and isolate sour water 17, discharge system carries out sewage disposal;
Adopt thermal low-pressure separators 30 to carry out thermal low separation to described hot high score oil 7 and obtain heat low point of gas 9 and heat low point of oil, and isolate sour water 18, discharge system carries out sewage disposal;
(5) using a part oily for low point of step (4) described heat as first burst of heat low point of oil 10 return step (1) and described coal tar 1, recycle hydrogen 3 mix and together with carry out described the first step hydrofining reaction;
Under hydrocracking catalyst exists, in hydrocracking reactor 31, carry out hydrocracking reaction after the recycle hydrogen 4 that the new hydrogen 2 residue oily for low point of step (4) described heat part inputted with make-up hydrogen compressor 35 as second burst of heat low point of oil 20, circulating hydrogen compressor 34 input mixes, obtain isocrackate 12;
Wherein, described hydrocracking catalyst comprises 8wt% nickel oxide, 22wt% Tungsten oxide 99.999, and surplus is silica support or alumina supporter; The heap of described hydrocracking catalyst is than being 0.85g/ml;
The pressure of described hydrocracking reaction is temperature is 360 DEG C, and pressure is 14Mpa, and hydrogen to oil volume ratio is 1500:1, and volume space velocity is 0.25h
-1;
(6) adopted by step (5) described isocrackate 12 cracking cold high pressure separator 32 to carry out cold anticyclone and be separated into cracking cold high score gas 15 and the cold high score oil 21 of cracking, and isolate sour water 14, discharge system carries out sewage disposal;
(7) in recycle hydrogen and cold hydrogen input step (1), described the first step hydrofining reaction is carried out together with being mixed by described to step (6) described cracking cold high score gas 15 and step (4) cold high score gas 11 also;
Adopt cold low separator 33 to carry out cold low after being mixed with the described cold high score of step (4) oily 13 by step (6) described cracking cold high score oil 21 to be together separated and to obtain cold low point of oil 37 and cold low point of gas 16, and isolate sour water 19, discharge system carries out sewage disposal;
(8) described for step (7) cold low point of oil 37, cold low point of gas 16 and step (4) described heat low point of gas 9 are mixed also input product separating unit 36 together and is separated, obtain gasoline products 22, diesel product 23 and hydrogenation tail oil 24; Described hydrocracking reaction is carried out afterwards by described hydrogenation tail oil 24 input step (5).
Embodiment 4
The present embodiment provides a kind of two-stage method coal tar hydrogenation process, and concrete steps are as follows:
(1) under Hydrobon catalyst exists, be incorporated in the first hydrofining reaction unit 25 carry out the first step hydrofining reaction by mixed to coal tar 1 and recycle hydrogen 3, obtain the first hydrotreated product 5;
Described first hydrofining reaction unit 25 comprises three identical first hydrofining reactors be arranged in series, described in each described first hydrofining reactor, the temperature of the first step hydrofining reaction is 370 DEG C, pressure is 14MPa, hydrogen to oil volume ratio is 1000:1, and volume space velocity is 1.0h
-1; The heap of hydrocracking catalyst described in described first hydrofining reactor is than being 0.8g/ml;
Described Hydrobon catalyst comprises 17wt% molybdenum oxide, 5wt% nickel oxide, and surplus is silica support or alumina supporter, and the pore volume of described Hydrobon catalyst is 0.4mL/g, and specific surface area is 185m
2/ g;
(2) described for step (1) the first hydrotreated product 5 is first passed into heat exchange refrigerating unit 26 to carry out heat exchange and be cooled to 330 DEG C; Afterwards under Hydrobon catalyst exists, the first hydrotreated product 5 after described heat exchange cooling process is carried out second step hydrofining reaction at the second hydrofining reaction unit 27, obtains second step hydrotreated product 6;
The temperature of described second step hydrofining reaction is 370 DEG C, and pressure is 14MPa, and hydrogen to oil volume ratio is 1000:1, and volume space velocity is 1.0h
-1; The heap of hydrocracking catalyst described in described second hydrofining reactor is than being 0.7g/ml;
Described Hydrobon catalyst comprises 17wt% molybdenum oxide, 5wt% nickel oxide, and surplus is silica support or alumina supporter, and the pore volume of described Hydrobon catalyst is 0.4mL/g, and specific surface area is 185m
2/ g;
(3) adopted by step (2) described second step hydrotreated product 6 high pressure hot separator 28 to carry out thermal high separation and obtain hot high score gas 8 and hot high score oil 7;
(4) adopted by described for step (3) hot high score gas 8 refining cold high pressure separator 29 to carry out cold anticyclone separation and obtain cold high score gas 11 and cold high score oil 13, and isolate sour water 17, discharge system carries out sewage disposal;
Adopt thermal low-pressure separators 30 to carry out thermal low separation to described hot high score oil 7 and obtain heat low point of gas 9 and heat low point of oil, and isolate sour water 18, discharge system carries out sewage disposal;
(5) using a part oily for low point of step (4) described heat as first burst of heat low point of oil 10 return step (1) and described coal tar 1, recycle hydrogen 3 mix and together with carry out described the first step hydrofining reaction;
Under hydrocracking catalyst exists, in hydrocracking reactor 31, carry out hydrocracking reaction after the recycle hydrogen 4 that the new hydrogen 2 residue oily for low point of step (4) described heat part inputted with make-up hydrogen compressor 35 as second burst of heat low point of oil 20, circulating hydrogen compressor 34 input mixes, obtain isocrackate 12;
Wherein, described hydrocracking catalyst comprises 8wt% nickel oxide, 22wt% molybdenum oxide, and surplus is silica support or alumina supporter; The heap of described hydrocracking catalyst is than being 0.80g/ml;
The pressure of described hydrocracking reaction is temperature is 390 DEG C, and pressure is 16Mpa, and hydrogen to oil volume ratio is 2000:1, and volume space velocity is 0.5h
-1;
(6) adopted by step (5) described isocrackate 12 cracking cold high pressure separator 32 to carry out cold anticyclone and be separated into cracking cold high score gas 15 and the cold high score oil 21 of cracking, and isolate sour water 14, discharge system carries out sewage disposal;
(7) in recycle hydrogen input step (1), described the first step hydrofining reaction is carried out together with being mixed by described to step (6) described cracking cold high score gas 15 and step (4) cold high score gas 11 also;
Adopt cold low separator 33 to carry out cold low after being mixed with the described cold high score of step (4) oily 13 by step (6) described cracking cold high score oil 21 to be together separated and to obtain cold low point of oil 37 and cold low point of gas 16, and isolate sour water 19, discharge system carries out sewage disposal;
(8) described for step (7) cold low point of oil 37, cold low point of gas 16 and step (4) described heat low point of gas 9 are mixed also input product separating unit 36 together and is separated, obtain gasoline products 22, diesel product 23 and hydrogenation tail oil 24; Described hydrocracking reaction is carried out afterwards by described hydrogenation tail oil 24 input step (5).
Embodiment 5
The present embodiment provides a kind of two-stage method coal tar hydrogenation process, and concrete steps are as follows:
(1) under Hydrobon catalyst exists, be incorporated in the first hydrofining reaction unit 25 carry out the first step hydrofining reaction by mixed to coal tar 1 and recycle hydrogen 3, obtain the first hydrotreated product 5;
Described first hydrofining reaction unit 25 comprises three identical first hydrofining reactors be arranged in series, described in each described first hydrofining reactor, the temperature of the first step hydrofining reaction is 390 DEG C, pressure is 18Mpa, hydrogen to oil volume ratio is 2000:1, and volume space velocity is 0.3h
-1; The heap of hydrocracking catalyst described in described first hydrofining reactor is than being 0.7g/ml;
Described Hydrobon catalyst comprises 17wt% molybdenum oxide, 5wt% nickel oxide, and surplus is silica support or alumina supporter, and the pore volume of described Hydrobon catalyst is 0.4mL/g, and specific surface area is 185m
2/ g;
(2) described for step (1) the first hydrotreated product 5 is first passed into heat exchange refrigerating unit 26 to carry out heat exchange and be cooled to 330 DEG C; Afterwards under Hydrobon catalyst exists, the first hydrotreated product 5 after described heat exchange cooling process is carried out second step hydrofining reaction at the second hydrofining reaction unit 27, obtains second step hydrotreated product 6;
The temperature of described second step hydrofining reaction is 390 DEG C, and pressure is 18Mpa, and hydrogen to oil volume ratio is 2000:1, and volume space velocity is 0.3h
-1; The heap of hydrocracking catalyst described in described second hydrofining reactor is than being 0.6g/ml;
Described Hydrobon catalyst comprises 17wt% molybdenum oxide, 5wt% nickel oxide, and surplus is silica support or alumina supporter, and the pore volume of described Hydrobon catalyst is 0.4mL/g, and specific surface area is 185m
2/ g;
(3) adopted by step (2) described second step hydrotreated product 6 high pressure hot separator 28 to carry out thermal high separation and obtain hot high score gas 8 and hot high score oil 7;
(4) adopted by described for step (3) hot high score gas 8 refining cold high pressure separator 29 to carry out cold anticyclone separation and obtain cold high score gas 11 and cold high score oil 13, and isolate sour water 17, discharge system carries out sewage disposal;
Adopt thermal low-pressure separators 30 to carry out thermal low separation to described hot high score oil 7 and obtain heat low point of gas 9 and heat low point of oil, and isolate sour water 18, discharge system carries out sewage disposal;
(5) using a part oily for low point of step (4) described heat as first burst of heat low point of oil 10 return step (1) and described coal tar 1, recycle hydrogen 3 mix and together with carry out described the first step hydrofining reaction;
Under hydrocracking catalyst exists, in hydrocracking reactor 31, carry out hydrocracking reaction after the recycle hydrogen 4 that the new hydrogen 2 residue oily for low point of step (4) described heat part inputted with make-up hydrogen compressor 35 as second burst of heat low point of oil 20, circulating hydrogen compressor 34 input mixes, obtain isocrackate 12;
Wherein, described hydrocracking catalyst comprises 8wt% nickel oxide, 22wt% cobalt oxide, and surplus is silica support or alumina supporter; The heap of described hydrocracking catalyst is than being 0.70g/ml;
The pressure of described hydrocracking reaction is temperature is 390 DEG C, and pressure is 16Mpa, and hydrogen to oil volume ratio is 2000:1, and volume space velocity is 0.5h
-1;
(6) adopted by step (5) described isocrackate 12 cracking cold high pressure separator 32 to carry out cold anticyclone and be separated into cracking cold high score gas 15 and the cold high score oil 21 of cracking, and isolate sour water 14, discharge system carries out sewage disposal;
(7) in recycle hydrogen and cold hydrogen input step (1), described the first step hydrofining reaction is carried out together with being mixed by described to step (6) described cracking cold high score gas 15 and step (4) cold high score gas 11 also;
Adopt cold low separator 33 to carry out cold low after being mixed with the described cold high score of step (4) oily 13 by step (6) described cracking cold high score oil 21 to be together separated and to obtain cold low point of oil 37 and cold low point of gas 16, and isolate sour water 19, discharge system carries out sewage disposal;
(8) described for step (7) cold low point of oil 37, cold low point of gas 16 and step (4) described heat low point of gas 9 are mixed also input product separating unit 36 together and is separated, obtain gasoline products 22, diesel product 23 and hydrogenation tail oil 24; Described hydrocracking reaction is carried out afterwards by described hydrogenation tail oil 24 input step (5).
Comparative example 1
This comparative example provides a kind of coal tar hydrogenation process, and concrete steps are as follows:
(1) in presence of hydrogen, coal tar enters hydrofining reaction district, contacts successively carry out hydrofining reaction with hydrogenation protecting catalyst with Hydrobon catalyst; The temperature of described hydrofining reaction is 390 DEG C, and pressure is 16Mpa, and hydrogen to oil volume ratio is 1500:1, and volume space velocity is 0.5h
-1, the heap ratio of Hydrobon catalyst described in each described hydrofining reactor is 0.9060g/ml;
Described Hydrobon catalyst comprises 17wt% molybdenum oxide, 5wt% nickel oxide, and surplus is silica support or alumina supporter, and the pore volume of described Hydrobon catalyst is 0.4mL/g, and specific surface area is 185m
2/ g;
(2) the generation oil of step (1) hydrofining gained carries out gas-liquid separation through high pressure hot separator;
(3) liquid product that step (2) high pressure hot separator separates enters thermal low-pressure separators and carries out further gas-liquid separation, and the heat that thermal low-pressure separators separates low point of oil is partly recirculated to hydrofining reaction district;
(4) step (3) remainder heat low point of oil enters hydrocracking reaction district, in presence of hydrogen, takes off after Pd/carbon catalyst to contact with hydrocracking catalyst and react successively, obtain isocrackate through Hydrobon catalyst, hydrogenation; The temperature of described hydrocracking reaction is 405 DEG C, and pressure is 16Mpa, and hydrogen to oil volume ratio is 1500:1, and volume space velocity is 0.5h
-1, the heap of described hydrocracking catalyst is than being 0.9420g/ml;
Described hydrocracking catalyst comprises 8wt% nickel oxide, 22wt% Tungsten oxide 99.999, and surplus is silica support or alumina supporter;
(5) step (4) gained isocrackate with enter cold high pressure separator from the isolated gas of high pressure hot separator;
(6) liquid that separates of step (5) cold high pressure separator and the isolated gas of thermal low-pressure separators enter cold low separator;
(7) the isolated liquid of step (6) cold low separator is after product stripping tower stripping, and stripping tower bottom liquid removes product separation column, obtains gasoline and diesel oil distillate.
It should be noted that, the coal tar that embodiment of the present invention 1-5 and comparative example 1 adopt comprises carbolineum, middle coalite tar and other coal-based pyrolysis oil cuts, and described coal tar oil properties is in table 1.
Coal tar oil properties described in table 1 embodiment 1-5 and comparative example 1
| Project | Index |
| Density (20 DEG C)/g.cm -3 | 1.13 |
| IBP/10％ | 210/311 |
| 30％/50％ | 332/349 |
| 70％/90 | 372/411 |
| 95％/EBP | 430/477 |
| S/μg.g -1 | 7000 |
| N/μg.g -1 | 10000 |
| Saturated point/wt% | 2.72 |
| Fragrance divides/wt% | 73.70 |
| Colloid/wt% | 22.94 |
| Bituminous matter/wt% | 0.64 |
Experimental example
Product oil (comprising gasoline and diesel oil distillate) number consecutively embodiment 1-5 and comparative example 1 prepared is A-F, and detect the composition of above-mentioned each cut, detected result is in table 2.
The different hydrogenation technique of table 2-prepares the composition analysis of gasoline and diesel oil
Data as can be seen from table 2, two-stage method hydrogenation technique of the present invention prepares gasoline and diesel oil (sample A-E) total recovery is higher, and product oil quality is good, and aromatic content of diesel oil is lower, and diesel cetane-number is relatively high; And the gasoline that comparative example hydrogenation technique prepares and diesel oil (sample F) total recovery low, product oil quality is lower, and aromatic content of diesel oil is up to being 30.2%.
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 two-stage method coal tar hydrogenation process, it comprises the steps:
(1) under Hydrobon catalyst exists, coal tar first carries out the first step hydrofining reaction at 360-400 DEG C, obtain the first step hydrofining reaction product and be cooled to 300-350 DEG C through heat exchange refrigerating unit, again second step hydrofining reaction is carried out to the first step hydrofining reaction product after cooling, obtain second step hydrotreated product;
(2) step (1) described second step hydrotreated product is separated through high pressure hot separator and obtains hot high score gas and hot high score oil;
(3) the described hot high score gas of step (2) is separated through cold high pressure separator and obtains cold high score gas and cold high score oil, and the described hot high score oil of step (2) is separated through thermal low-pressure separators and obtains heat low point of gas and heat low point of oil;
(4) part oily for low point of step (3) described heat is returned step (1) and described coal tar mix and together with carry out described the first step hydrofining reaction;
Under hydrocracking catalyst exists, a residue part oily to low point of step (3) described heat carries out hydrocracking reaction, obtains isocrackate;
(5) step (4) described isocrackate is separated through cold high pressure separator and obtains cracking cold high score gas and the cold high score oil of cracking;
(6) be separated through cold low separator together after described to step (5) described cracking cold high score oil and step (3) cold high score oil being mixed and obtain cold low point of oil and cold low point of gas;
(7) described for step (6) cold low point of oil, cold low point of gas and step (3) described heat low point of gas are mixed also input product separating unit together and is separated, obtain gasoline products, diesel product and hydrogenation tail oil.
2. two-stage method coal tar hydrogenation process according to claim 1, it is characterized in that, described the first step hydrofining reaction carries out at the first hydrofining reaction unit, described second step hydrofining reaction carries out at the second hydrofining reaction unit, described first hydrofining reaction units in series arranges 3-4 hydrofining reactor, and described second hydrofining reaction unit arranges 1 hydrofining reactor.
3. two-stage method coal tar hydrogenation process according to claim 1 and 2, is characterized in that, the pressure of described the first step hydrofining reaction is 14-18MPa, and hydrogen to oil volume ratio is 1000:1-2000:1, and volume space velocity is 0.3-1.5h
-1;
The pressure of second step hydrofining reaction is 14-18MPa, and hydrogen to oil volume ratio is 1000:1-2000:1, and volume space velocity is 0.3-1.5h
-1.
4. according to the arbitrary described two-stage method coal tar hydrogenation process of claim 1-3, it is characterized in that, the heap of hydrocracking catalyst described in described first hydrofining reactor is than being 0.7-0.8g/ml, and the heap of hydrocracking catalyst described in described second hydrogenator is than being 0.6-0.7g/ml.
5., according to the arbitrary described two-stage method coal tar hydrogenation process of claim 1-4, it is characterized in that, in step (1), described Hydrobon catalyst is with one or both in Mo or Ni for active ingredient, take aluminum oxide as carrier; The pore volume 0.20-0.50mL/g of described Hydrobon catalyst, specific surface area 100-200m
2/ g.
6. according to the arbitrary described two-stage method coal tar hydrogenation process of claim 1-5, it is characterized in that, in step (4), the heap of described hydrocracking catalyst is than being 0.65-0.85g/ml.
7. according to the arbitrary described two-stage method coal tar hydrogenation process of claim 1-6, it is characterized in that, in step (4), described hydrocracking catalyst is with any one or a few in Mo, W, Co or Ni for active ingredient, with aluminum oxide and/or silicon oxide for carrier.
8. according to the arbitrary described two-stage method coal tar hydrogenation process of claim 1-7, it is characterized in that, the pressure of described hydrocracking reaction is temperature is 360-420 DEG C, and pressure is 14-18Mpa, hydrogen to oil volume ratio is 1500:1-2500:1, and volume space velocity is 0.25-0.75h
-1.
9. according to the arbitrary described two-stage method coal tar hydrogenation process of claim 1-8, it is characterized in that, as the recycle hydrogen of hydrocracking in hydrofining in step (1) and step (4) and cold hydrogen together with step (5) described cracking cold high score gas and the described cold high score gas of step (3) being mixed also.
10., according to the arbitrary described two-stage method coal tar hydrogenation process of claim 1-9, it is characterized in that, carry out described hydrocracking reaction by all or part of input step (4) of step (7) described hydrogenation tail oil.
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| CN107987882A (en) * | 2016-10-27 | 2018-05-04 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking for mixing artificial coal tar |
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| JPH07316566A (en) * | 1994-05-27 | 1995-12-05 | Nippon Oil Co Ltd | Hydrogenation treatment of heavy oil |
| CN102041087A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Hydrocracking method of deep cut anthracene oil |
| CN103849432A (en) * | 2012-11-28 | 2014-06-11 | 何巨堂 | Combined method for processing coal tar |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07316566A (en) * | 1994-05-27 | 1995-12-05 | Nippon Oil Co Ltd | Hydrogenation treatment of heavy oil |
| CN102041087A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Hydrocracking method of deep cut anthracene oil |
| CN103849432A (en) * | 2012-11-28 | 2014-06-11 | 何巨堂 | Combined method for processing coal tar |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107987882A (en) * | 2016-10-27 | 2018-05-04 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking for mixing artificial coal tar |
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