CN101333448B - Direct liquefaction process of coal by replacing circling solvent with petroleum or petroleum refining byproduct - Google Patents

Direct liquefaction process of coal by replacing circling solvent with petroleum or petroleum refining byproduct Download PDF

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CN101333448B
CN101333448B CN2008101163477A CN200810116347A CN101333448B CN 101333448 B CN101333448 B CN 101333448B CN 2008101163477 A CN2008101163477 A CN 2008101163477A CN 200810116347 A CN200810116347 A CN 200810116347A CN 101333448 B CN101333448 B CN 101333448B
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oil
coal
liquefaction
petroleum
quality
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CN101333448A (en
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李克健
李文博
朱晓苏
张晓静
赵鹏
史士东
何平
王雨
杜淑凤
高振楠
胡发亭
谷小会
李培霖
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煤炭科学研究总院
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Abstract

The invention relates to a coal direct liquefaction method using petroleum or petroleum refining byproducts to replace a cycling solvent, which comprises processes of: replacing or partially replacing the traditional coal liquefied cycling solvent by low quality petroleum with high metal and asphaltene content and heavy oil, as well as petroleum refining byproducts such as catalytic cracking heavy recycle stock, clarified oil and outside throwing slurry oil, preparing coal slurry by co-catalyst sulfur and high-activity Gamma-hydrated iron oxide type liquefaction catalyst, then implementing the coal direct liquefaction and hydrogenation, finally obtaining light and medium distillate oil, the coal conversion is increased by 1 percent to 5 percent, the yield of generated oil products is increased by 5 percent to 40 percent, the sedimentation and coking in a reactor are reduced, also the utilization value of low value-added petroleum and petroleum refining byproducts is greatly increased, and economic benefits of coal direct liquefaction are increased. The method can be widely used for coal direct liquefaction.

Description

A kind of coal direct liquefaction method that substitutes circulating solvent with oil or refining of petroleum sub product
Technical field
The present invention relates to the coal direct liquefaction field, particularly relate to the coal direct liquefaction method that substitutes circulating solvent with oil or refining of petroleum sub product.
Technical background
Coal is the abundantest in the world solid mineral fuel, and it is wide to distribute, and reserve is big, can exploit in a large number; Yet the utilization of coal is used as fuel with solid raw coal form always, seldom processes refining, and this is that molecule is with cyclic aromatic compounds such as monocycle, dicyclo, three rings in the coal because the chemical structure of coal own is extremely complicated; Particularly the macromole of condensed-nuclei aromatics or heterocyclic arene is formed, and this ring-type macromolecular structure is stable, is difficult to pyrolysis liquefying, and for example USP 5336395 discloses a kind of method of gelatin liquefaction; This method is carried out in two steps, at first coal is mixed with CO and water, under HTHP, carries out pre-treatment, then in the presence of solvent and catalyzer; With pretreated coal under higher temperature and hydrogen pressure, liquefy product liquid, this method and technology is complicated, condition is harsh; Need a large amount of hydrogen of outside supply, investment is big, and cost is high.
Got into since 21st century; Along with whole world petroleum resources and Sweet natural gas are constantly exploited; Resource reduces day by day; Spurt in prices, can obtain replacing the liquid product of oil maybe can replace the geseous fuel of Sweet natural gas is that main gelatin liquefaction technology receives countries in the world, especially receives the relatively special favor of the abundant country of poorness and coal resource of petroleum resources.
Present existing coal direct liquefaction technology; The described Exxon of USP4048054 hydrogen supply dissolvent technology for example; The described Catalytic two-stage of USP4842719 coal hydrogenation andhydroconversion process; DCL/Direct coal liquefaction technology of Chinese patent ZL 03102672.9 described a kind of adverse current, circulation gelatin liquefaction reactors in series or the like; Although these DCL/Direct coal liquefaction technology technological processs are different, their something in common is: the coal slurry of its DCL/Direct coal liquefaction technology prepare that solvent for use adopts all that DCL/Direct coal liquefaction process self produces in, heavy ends is as circulating solvent.Circulating solvent its mainly form be 2~4 the ring aromatic hydrocarbons and hydrogenation of aromatics.In the DCL/Direct coal liquefaction process, the internal circulating load of solvent is bigger, and 200~320 ℃ of distillate content are more than 50% in the circulating solvent, and matter oil can be used to the diesel oil of production high added value in this part.This part lighter fraction oil can not influence the economy of DCL/Direct coal liquefaction process as product in the circulating solvent; And constantly recycling the further lighting of meeting in the process; Destroy the stability of coal oil mixture, its consequence is serious in the vaporization of DCL/Direct coal liquefaction reactor drum internal solvent, causes liquid-solid phase concentration too high and deposit; Influence the reaction effect of DCL/Direct coal liquefaction, also can cause reactor plugs when serious.
At present, in petroleum refining process, catalytic cracking, coking, lubricating oil aromatic extraction unit all are the important operating units of refinery.In the extraction aromatic hydrocarbons of the extraction aromatic hydrocarbons of the heavy recycle stock in the CCU, clarified oil, externally extracting oil, heavy recycle stock, the extraction aromatic hydrocarbons of externally extracting oil, wax tailings, the distillates such as extraction aromatic hydrocarbons of lubricating oil aromatic extraction unit; Be difficult to continue deep processing owing to containing a large amount of aromatic hydrocarbons, oil or sell as low grade products usually acts as a fuel.In addition; The low-quality oil and the heavy oil thereof of some high metal content, high asphalt content; Owing to contain more metal and bituminous matter; Occur significantly deposition and coking tendency in the conventional course of processing easily,, increased the severity of petroleum refining process catalyzer work-ing life in the petroleum refining process and quality product causing influence in various degree.
Summary of the invention
The objective of the invention is to overcome the shortcomings and deficiencies that above-mentioned prior art exists; Be engaged in the development research and the long-term practice of DCL/Direct coal liquefaction for many years through the contriver, exploitation provides a kind of coal direct liquefaction method that substitutes circulating solvent with oil or refining of petroleum sub product.
A kind of coal direct liquefaction method with oil or the alternative circulating solvent of refining of petroleum sub product provided by the invention is characterized in that comprising the following steps:
1. the preparation of coal slurry
With water-content is 0.5 to 4.0 quality %, granularity (or claiming particle diameter, i.e. particle dia)<0.15mm coal dust; Water-content 0.5~4.0 quality %, diameter is the 20-50 nanometer, length is the γ-aqua oxidation swage high reactivity DCL/Direct coal liquefaction catalyzer of 80-150 nanometer ultra-fine grain; Promotor, oil or refining of petroleum sub product and gelatin liquefaction circulating solvent, thorough mixing is processed coal slurry; Wherein the S/Fe mol ratio is 1-4, and the Fe/ dry coal is 0.5-2.0 quality %, coal slurry solids concn 20-55 quality %.
2. the direct liquefaction of coal
With step 1. coal slurry in the DCL/Direct coal liquefaction reactor drum, at H 2Carry out liquefaction reaction in the atmosphere, temperature of reaction 430-465 ℃, reaction pressure 15-19MPa; Wherein the hydrogen dividing potential drop is greater than 80%; The residence time is 30 to 120 minutes, and reaction product obtains liquid-solid phase high score oil, low oil and the hydrogen-rich gas of dividing of liquid phase after high temperature, LTS separate, and hydrogen-rich gas is as recycle hydrogen; Behind the frequent pressure fractionating of liquid-solid phase high score oil; Get cat head liquefaction benzoline, the tower bed material carries out vacuum fractionation and gets liquefied residue and liquefied heavy distillate, and liquefaction benzoline and liquefied heavy distillate are mixed into the mixed liquefied raw oil that generates oil as hydrogenation reaction.
3. hydrogenation
Step mixed liquefied generation 2. is oily in hydrogenator, at H 2Carry out hydrogenation in the atmosphere, hydrogenation catalyst is a present petroleum industry Hydrobon catalyst (commercially available prod) commonly used, temperature of reaction 330-390 ℃; Reaction pressure 10-19MPa, wherein the hydrogen dividing potential drop is greater than 85%.Hydrogenation products gets lightweight raw naphtha cut, gas oil fraction and circulation hydrogen supply dissolvent oil after separating fractionation.
According to oil described in a kind of coal direct liquefaction method (abbreviation present method) that substitutes circulating solvent with oil or refining of petroleum sub product provided by the invention or the refining of petroleum sub product substitutes or the alternative DCL/Direct coal liquefaction process circulating solvent of part; The low-quality oil that comprises for example high metal content, high asphalt content; Or recycle stock, clarified oil or the slurry oil (externally extracting oil) of refinery catalyzed cracking processing process; The extraction oil of the residual oil of refinery atmospheric vacuum distillation process, refinery Process of Lube Solvent Refining; The extraction aromatic hydrocarbons of refinery catalytic cracking recycle oil solvent extractive process, coking heavy oil, viscosity breaking heavy oil or hydrogen cracking heavy oil etc. are preferably recycle stock, clarified oil, slurry oil with refinery catalyzed cracking processing process; More preferably use the slurry oil of refinery catalyzed cracking processing process, these oil product aromaticity contents are greater than 40 quality %.
The sub product of said oil or petroleum refining process, low value-added especially sub product, its boiling range is for being 980.0-1150.0kg/m greater than 220 ℃, density 3, aromaticity content is greater than 40 quality %.
Coal slurry transport condition according to the DCL/Direct coal liquefaction technological process requires and used petroleum refining process sub product kind and process characteristic, and the addition of oil or refining of petroleum sub product is 100%-5% with the ratio of circulating solvent quality, is preferably 75%-5%.
In these oil or the refining of petroleum sub product distillate, be difficult to continue deep processing owing to containing a large amount of aromatic hydrocarbons, the oil or sell as low grade products of acting as a fuel usually is so also claim refining of petroleum low value-added sub product.In addition; The low-quality oil and the heavy oil thereof of some high metal content, high asphalt content; Owing to contain more metal and bituminous matter, occur significantly deposition and coking tendency in the conventional course of processing easily, to catalyzer work-ing life in the petroleum refining process and quality product causing influence in various degree; Increased the severity of petroleum refining process, yet research shows that this type heavy crude or distillate but are the solvent oil cuts of ideal DCL/Direct coal liquefaction.
The low value-added sub product distillate that contains a large amount of aromatic hydrocarbons in present method in the low-quality oil of high metal content, high asphalt content or the above-mentioned refining of petroleum course of processing substitutes the partly or entirely middle matter component in the circulating solvent; Both can improve the performance of circulating solvent; Effectively prevent the circulating solvent lighting; Can this part unmanageable low value-added distillate be found a new processing approach again; Thereby obtain more diesel oil distillate, improved DCL/Direct coal liquefaction high value added product-vapour, diesel yield, improved the economic benefit of coal liquefaction plant greatly.
Said circulating solvent is in the DCL/Direct coal liquefaction production process, and the solvent that coal liquification device continuous operation process is used is the middle matter oil of DCL/Direct coal liquefaction self generation and the mixture of BO, is called process solvent or circulating solvent.Can improve the hydrogen supply capacity of solvent through the method for the preparatory hydrogenation of solvent.The main composition of circulating solvent is the aromatic hydrocarbons and the hydrogenation of aromatics of 2~4 rings.In the DCL/Direct coal liquefaction process, the internal circulating load of solvent is bigger, and 200~320 ℃ of distillate content are more than 50% in the circulating solvent, and matter oil can be used to the diesel oil of production high added value in this part.Yet this part lighter fraction oil can not influence the economy of gelatin liquefaction process as product in the circulating solvent; And constantly recycling the further lighting of meeting in the process, and destroy the stability of coal oil mixture, its consequence is to cause the vaporization of gelatin liquefaction reactor drum internal solvent serious; Cause liquid-solid phase concentration too high and deposit; Influence the reaction effect of gelatin liquefaction, also can cause reactor plugs when serious, and reduce lightweight or middle matter oil distillate processed oil output.
Said coal dust is the coal with various metamorphic grade, and for example younger bituminous, brown coal or mud coal etc. are preferably brown coal or younger bituminous; It is 0.5~4.0 quality % that pulverizing is dried to water-content; Granularity<0.15mm, it is even to help dispersing and mixing, can fully liquefy; Shorten liquefying time, improve the liquiefied product yield.
Said γ-hydrous iron oxide high reactivity DCL/Direct coal liquefaction catalyzer mainly consists of γ-FeOOH; Iron level 3-8 quality % wherein, coal 40-90 quality %, the ferrum-based catalyst particle is dispersed in the coal dust surface; Long-term stability sees Chinese patent ZL03153377.9 for details.
Said promotor is sulphur or sulfocompound etc., is preferably sulphur.To make the S/Fe mol ratio be 1-4 to these material add-ons in the said coal slurry, is preferably 2, and wherein S is meant sulphur atom in sulphur or the sulfocompound of promotor.Fe/ dry coal mass ratio is 0.5%-2.0%, is preferably 0.5%, and wherein Fe represents in the DCL/Direct coal liquefaction catalyzer Fe in γ-hydrous iron oxide.The coal slurry solids concn is 20-55 quality %, is preferably 45 quality %.
The advantage of the inventive method is:
1. a kind of coal direct liquefaction method that substitutes circulating solvent with oil or refining of petroleum sub product of providing of present method; The oil plant wide material sources of used low-quality oil or the low value-added all or part of alternative circulating solvent of refining of petroleum sub product and cheapness, especially refinery oil slurry from catalytically cracked heavy oil are because the refinery catalytically cracked oil is except that the part freshening at present; All the other get rid of outward; The amount of getting rid of is decided according to operating conditions outward, and general externally extracting oil accounts for the 3%-10% of recycle stock, and the annual FCC externally extracting oil of China is up to more than 3,000,000 tons; Externally extracting oil acts as a fuel basically and burns, and utility value is not high.
2. present method can make the transformation efficiency of coal improve 0.5%-5%; When the oil plant of especially alternative circulating solvent is the refinery oil slurry from catalytically cracked heavy oil; Can make the transformation efficiency of coal improve 1%-5%; Mainly be because in the gelatin liquefaction reaction process; The low value-added sub product and the coal hydrogenation of the petroleum refining process of introducing have synergy, are that this part catalyzer has quickened the macromolecular further cracking after coal and the coal cracking because contain catalytic cracking catalyst in the replace solvents catalytically cracked oil that is added in addition.
3. present method is that high aromaticity contents of this type such as FCC slurry oil and high boiling petroleum by-product have been sought a new processing approach, promptly is processed into the diesel oil distillate of high added value as the substitute of coal Direct Hydrogenation liquefaction process solvent.
4. present method can make light, the middle matter of gelatin liquefaction give birth to olefiant yield raising 5%-40%, can improve the economic benefit of DCL/Direct coal liquefaction factory greatly.
5. present method can suppress or reduce the deposition and the coking of material in the DCL/Direct coal liquefaction technological process reactor drum to a certain extent; When especially being recycle stock, clarified oil and the slurry oil of refinery catalyzed cracking processing process as the oil plant that substitutes circulating solvent, it is better that it suppresses coking effect.
Description of drawings
Fig. 1 is the process flow sheet of method provided by the present invention.Illustrate: 1, hydrogen, 2, through being dried and crushed into the raw material coal dust of certain particle size, 3, the high reactivity catalyst for coal liquefaction, 4, promotor; 5, oil or refining of petroleum sub product, 6, coal slurry preparation jar, 7, the gelatin liquefaction reactor drum, 8, high-temperature separator; 9, LTS, 10, atmospheric fractional tower, 11, the vacuum fractionation tower, 12, liquefied residue; 13, hydrogenator, 14 vapour liquid separators, 15, the product separation column, 16, liquefaction raw naphtha cut; 17, liquefaction gas oil fraction, 18, liquefied circulating solvent, 19, recycle hydrogen.
Embodiment
The present invention further specifies the present invention with the following example and accompanying drawing, but protection scope of the present invention is not limited to the following example.
Embodiment 1,2 and comparative example 1
In the present embodiment, as the gelatin liquefaction feed coal, the character of this bituminous coal is seen table 1 with bituminous coal.Daf is meant moisture-and-ash-free basis (daf, dry and ash free) in the table 1, down together.The slurry oil that gets rid of outward with factory of petrochemical refining CCU is as the plus solvent that substitutes the DCL/Direct coal liquefaction circulating solvent, and the character of externally extracting oil is seen table 2.Select the catalyzer according to the synthetic preparation of the method among the patent ZL03153377.9 " a kind of high dispersive iron-based DCL/Direct coal liquefaction Catalysts and its preparation method " for use, its character is seen table 3.The Hydrobon catalyst that is with commercially available Ni-Mo generates oil (IBP-530 ℃) hydrogenation catalyst as liquefaction.
Table 1 bituminous coal coal analysis data
Table 2 catalytic cracking externally extracting oil character
Project The catalytic cracking externally extracting oil
Density (20 ℃), kg/m 3 994.5
Elementary composition, % (quality)
?C 88.01
?H 11.02
?S 0.54
?N 0.42
Boiling range, ℃
?IBP 207
?10vol% 380
?30vol% 468
?50vol% 500
Carbon residue, % 7.14
The cracking catalysis agent content, g/L 1.6
Form % (quality)
Stable hydrocarbon 39.3
Aromatic hydrocarbons 45.5
Colloid 8.1
Bituminous matter 7.1
Table 3 gelatin liquefaction effective catalyst character
Project
Iron (quality %) 6.71
Coal (quality %) 84.72
Water (quality %) 3.81
Other (quality %) 4.76
Shape Spindle body
Granularity Long: 80-150nm, diameter: 30-50nm
Present embodiment 1,2; In the comparative example 1; Through being dried and crushed into water-content is 2.86% (quality), and a kind of bituminous coal of granularity<0.15mm, process are synthesized preparation and be ground into water-content is 3.81% (quality), and diameter is the 30-50 nanometer; Length is that (type of γ-FeOOH) liquefaction high activated catalyst, promotor are that sulphur, the oil that substitutes the DCL/Direct coal liquefaction circulating solvent or the low value-added sub product of petroleum refining process are catalytic cracking externally extracting oil and DCL/Direct coal liquefaction circulating solvent for the γ-hydrous iron oxide of the ultra-fine grain of 80-150 nanometer; Thorough mixing is processed coal slurry in coal slurry preparation jar 6 in proportion, wherein, and S/Fe (mol ratio)=2; The Fe/ dry coal is 0.5% (quality), coal slurry solids concn 45% (quality).Coal slurry and hydrogen 1 get into two-stage tandem liquefying reactor 7 continuously and carry out the gelatin liquefaction reaction after preheating, reactor drum is a bubbling bed reactor, and the resultant of reaction material gets into high-temperature separator 9; Control high-temperature separator temperature is 380 ℃, and the high-temperature separator gaseous phase materials gets into LTS 10, and control low ternperature separation process actuator temperature is a room temperature; LTS 10 gas phases part is used as recycle hydrogen; Redundance is discharged system, and high-temperature separator 9 carries out normal pressure with the liquid phase part entering atmospheric fractional tower 11 of LTS 10 to be separated, and isolates light ends; Atmospheric tower 11 substrate material get into vacuum fractionation tower 12 and carry out the separation of solid-liquid phase; Vacuum distillation tower 12 substrate feed liquid residues, cat head is isolated the liquefied heavy distillate, and the residue of underpressure distillation contains amount of solid and is controlled at 50-55% (quality); Atmospheric fractional tower 11 isolated light ends and vacuum distillation tower 12 isolated liquefied heavy distillates and hydrogen are mixed into hydrogenator 13 and carry out catalytic hydrogenation reaction; Purpose is in order to improve the hydrogen supply performance of circulating solvent, and hydrogenator 13 resultant of reaction material are after gas-liquid separator 14 separates, and the gas phase part is used as recycle hydrogen; Redundance is discharged system, and the separator liquid phase materials gets into product separation column 15 and isolates raw naphtha cut 16, gas oil fraction 17 and hydrogen supply property circulating solvent 18.
Table 4 is to adopt process method of the present invention to add this bituminous coal autoclave liquefaction test result that 20% and 10% catalytic cracking externally extracting oil substitutes circulating solvent, and the productive rate data in the table serve as the calculating benchmark with daf base coal+externally extracting oil.
Table 4
Processing condition Example 1 Example 2
Temperature of reaction, ℃ 455 455
The hydrogen first pressing, MPa 10 10
Reaction times, min 60 60
Coal slurry is formed, quality %
Coal 45 45
The catalytic cracking externally extracting oil 20 10
Circulating solvent oil 35 45
The liquefaction test result, quality %
Transformation efficiency 97.70 94.51
The oil productive rate 77.35 72.71
The gas productive rate 13.23 13.02
The aquatic products rate 9.50 10.29
The hydrogen consumption 4.05 4.03
This bituminous coal autoclave liquefaction test result when table 5 is solvent-free alternative case of comparative example 1.
Table 5
Processing condition Comparative example 1
Temperature of reaction, ℃ 455
The hydrogen first pressing, MPa 10
Reaction times, min 60
Coal slurry is formed, quality %
Coal 45
Circulating solvent oil 55
The liquefaction test result, quality %
Transformation efficiency 91.83
The oil productive rate 64.18
The gas productive rate 14.96
The aquatic products rate 11.05
The hydrogen consumption 4.04
Can find out from table 4 and table 5: adopt the catalytic cracking externally extracting oil to substitute the direct circulating solvent of coal; Carry out autoclave gelatin liquefaction test; The oily yield of DCL/Direct coal liquefaction reaction is improved; Simultaneously the transformation efficiency of coal is improved greatly, and be the raising along with the ratio of substituting, oily yield and coal transformation efficiency are also along with significantly increasing.
Table 6 is to adopt the inventive method to add 20% and 10% the catalytic cracking externally extracting oil this bituminous coal continuous apparatus test-results that liquefies when substituting circulating solvent.Productive rate data in the table serve as to calculate benchmark with daf base coal+externally extracting oil.
Table 6
Processing condition Example 1 Example 2
Temperature of reaction, ℃ 460 460
Reaction pressure, MPa 19 19
Coal slurry is formed, quality %
Coal 45 45
The catalytic cracking externally extracting oil 10 20
Circulating solvent oil 45 35
The catalyzer addition, (Fe/ butt coal) % (quality) 0.5 0.5
The liquefaction test result, quality %
Transformation efficiency 91.51 92.13
The oil yield 62.83 68.73
The gas productive rate 14.62 14.78
The aquatic products rate 10.86 10.04
Raw naphtha cut productive rate 23.94 23.36
The gas oil fraction productive rate 38.89 45.37
The hydrogen consumption 4.86 4.62
Table 7 is this bituminous coal DCL/Direct coal liquefaction continuous apparatus test-results of solvent-free alternative case.Productive rate data in the table serve as to calculate benchmark with the daf coal.
Table 7
Processing condition Comparative example 1
Temperature of reaction, ℃ 460
Reaction pressure, MPa 19
Coal slurry is formed, quality %
Coal 45
Circulating solvent oil 55
The catalyzer addition, (Fe/ butt coal) % (quality) 0.5
Test-results, quality %
The liquefaction coal transformation efficiency 88.84
The oil yield 52.97
The gas productive rate 16.78
The aquatic products rate 11.92
Raw naphtha cut productive rate 22.13
The gas oil fraction productive rate 30.84
The hydrogen consumption 6.65
Can know from the data of table 6 and table 7: the ratio of catalytic cracking externally extracting oil replace solvents is 10% o'clock; The inventive method can make the transformation efficiency of coal bring up to 91.51% by 88.84%; Can make the yield of vapour, diesel oil distillate reach 62.83%, with regard to the oily yield of technological process, the inventive method has improved 9.86% than former method; If with the daf coal serves as to calculate benchmark; Then the yield of vapour, diesel oil distillate reaches 76.79% (daf coal), with the oily yield compared of table 7, actual be the fecund vapour, the diesel oil distillate of 23.82% (daf coal); When the ratio of catalytic cracking externally extracting oil replace solvents was 20%, the inventive method can make the transformation efficiency of coal bring up to 92.13% by 88.84%, can make the yield of vapour, diesel oil distillate reach 68.73%; With regard to the oily yield of technological process; The inventive method has improved 15.76% than former method, and as if serving as to calculate benchmark with the daf coal, then the yield of vapour, diesel oil distillate reaches 99.28% (daf coal); Oily yield compared with table 7; Actual be the fecund vapour, the diesel oil distillate of 46.31% (daf coal), realized solvent alternate purpose, can improve the economic benefit of DCL/Direct coal liquefaction factory greatly.
In the foregoing description; The transformation efficiency of coal is improved, and its major cause is in the DCL/Direct coal liquefaction reaction process, introduces the catalytic cracking externally extracting oil; This catalytic cracking externally extracting oil and coal have synergy; Be because contain the catalytic cracking catalyst of 1.6g/L in the replace solvents catalytic cracking externally extracting oil that is added in addition, played the catalytic cracking effect in the reaction process of DCL/Direct coal liquefaction, promoted the macromolecular further cracking after coal and the coal cracking.
Embodiment 3
Coal that present embodiment adopts, DCL/Direct coal liquefaction high activated catalyst, promotor, hydrogenation catalyst and technological process are identical with embodiment 1, and different is: low-quality a kind of heavy oil that the alternative DCL/Direct coal liquefaction circulating solvent of employing is high metal content, high asphalt content.The character of used heavy oil is seen table 8.
Table 9 is to adopt the inventive method to add 10% this heavy oil bituminous coal direct liquefaction continuous apparatus test-results when substituting circulating solvent.Productive rate data in the table serve as to calculate benchmark with daf base coal+heavy oil.
The character of table 8 heavy oil
Project Heavy oil
Density (20 ℃), kg/m 3 1043.5
Elementary composition, % (quality)
C 84.33
H 10.61
S 3.24
N 0.92
Metal content, ppm
Ni 44
V 680
Na 120
Ca 10
Form quality %
Stable hydrocarbon 13.15
Aromatic hydrocarbons 49.01
Colloid 16.13
Bituminous matter 21.71
Table 9
Processing condition Example 3
Temperature of reaction, ℃ 460
Reaction pressure, MPa 19
Coal slurry is formed, quality %
Coal 45
Heavy oil 10
Circulating solvent oil 45
The catalyzer addition, (Fe/ butt coal) % (quality) 0.5
The liquefaction test result
Transformation efficiency 90.29
The oil yield 60.69
The gas productive rate 12.48
The aquatic products rate 9.64
Raw naphtha cut productive rate 22.45
The gas oil fraction productive rate 38.24
The hydrogen consumption 5.02
The data of table 9 are compared with the data of table 7, can know: the ratio of heavy oil replace solvents is 10% o'clock, and the inventive method can make the transformation efficiency of coal bring up to 90.29% by 88.84%; Can make the yield of vapour, diesel oil distillate reach 60.69%, with regard to the oily yield of technological process, the inventive method has improved 7.72% than former process method; If with daf base coal serves as to calculate benchmark; Then the yield of vapour, diesel oil distillate reaches 74.18%, with the oily yield compared of table 7, and actual vapour, the diesel oil distillate of 21.21% (daf base coal) that be fecund; Realize solvent alternate purpose, can improve the economic benefit of DCL/Direct coal liquefaction factory greatly.
Embodiment 4
Coal that present embodiment adopts, DCL/Direct coal liquefaction high activated catalyst, promotor, hydrogenation catalyst and technological process are identical with embodiment 1; Different is: the oil of the alternative DCL/Direct coal liquefaction circulating solvent of employing or the low value-added sub product of petroleum refining process are a kind of extraction aromatic hydrocarbons after hydrotreatment, and its character is seen table 10.
Table 11 is to adopt the inventive method to add extraction aromatic hydrocarbons after 55% this hydrotreatment bituminous coal direct liquefaction continuous apparatus test-results when substituting circulating solvent.Productive rate data in the table serve as to calculate benchmark with daf coal+extraction aromatic hydrocarbons.
Table 10
Table 11
Processing condition Example 4
Temperature of reaction, ℃ 460
Reaction pressure, MPa 19
Coal slurry is formed, quality %
Coal 45
Extraction aromatic hydrocarbons after the hydrotreatment 55
Circulating solvent oil 0
The catalyzer addition, (Fe/ butt coal) % (quality) 0.5
The liquefaction test result, quality %
Transformation efficiency 90.55
The oil yield 77.65
The gas productive rate 8.13
The aquatic products rate 6.94
Raw naphtha cut productive rate 23.74
The gas oil fraction productive rate 53.91
The hydrogen consumption 4.62
The data of table 11 are compared with the data of table 7; Can know: the ratio of the extraction aromatic hydrocarbons replace solvents after a kind of hydrotreatment is 55% when being replacing whole, and the inventive method can make the transformation efficiency of coal bring up to 90.55% by 88.84%, can make the yield of vapour, diesel oil distillate reach 77.65%; With regard to the oily yield of technological process; The inventive method has improved 24.68% than former method, and as if serving as to calculate benchmark with the daf coal, then the yield of vapour, diesel oil distillate reaches 172.56% (daf coal); Oily yield compared with table 7; Actual vapour, the diesel oil distillate of 119.54% (daf coal) that be fecund realized the purpose of solvent replacing whole can improving the economic benefit of DCL/Direct coal liquefaction factory greatly.

Claims (3)

1. the coal direct liquefaction method with oil or the alternative circulating solvent of refining of petroleum sub product is characterized in that comprising the following steps:
1. the preparation of coal slurry
With coal dust, catalyst for coal liquefaction, promotor, oil or refining of petroleum sub product, with the gelatin liquefaction circulating solvent; Thorough mixing is processed coal slurry; Said coal dust is dried to the powdered granule that water-content is 0.5 to 4.0 quality %, granularity<0.15mm for pulverizing; Said catalyst for coal liquefaction be water-content be 0.5~4.0 quality %, load on the coal dust, diameter is the 20-50 nanometer, length is 80-150 nanometer ultra-fine grain γ-aqua oxidation swage high reactivity deliquescence accelerant; Said coal slurry is: the S/Fe mol ratio is 1-4, and the Fe/ dry coal is 0.5-2.0 quality %, solids concn 20-55 quality %; Said promotor is sulphur or sulfocompound;
2. the direct liquefaction of coal
With step 1. coal slurry in the DCL/Direct coal liquefaction reactor drum at H 2Carry out liquefaction reaction in the atmosphere, temperature of reaction 430-465 ℃, reaction pressure 15-19MPa; Wherein the hydrogen dividing potential drop is greater than 80%; The residence time is 30-120 minute, and reaction product obtains liquid-solid phase high score oil, low oil and the hydrogen-rich gas of dividing of liquid phase after high temperature, LTS separate, and hydrogen-rich gas is as recycle hydrogen; Behind the frequent pressure fractionating of liquid-solid phase high score oil; Get cat head liquefaction benzoline, the tower bed material carries out vacuum fractionation and gets liquefied residue and liquefied heavy distillate, and liquefaction is light, heavy distillate is mixed into the raw oil of liquefaction generation oil as hydrogenation reaction;
3. hydrogenation
With step mixed liquefied generation oil 2. in hydrogenator at H 2Hydrobon catalyst carries out hydrogenation, temperature of reaction 330-390 ℃ under existing in the atmosphere; Reaction pressure 10-19MPa, wherein the hydrogen dividing potential drop is greater than 85%, and hydrogenation products obtains lightweight raw naphtha cut, gas oil fraction and circulation hydrogen supply dissolvent oil after separating fractionation.
According to claim 1 substitute the circulating solvent coal direct liquefaction method with oil or refining of petroleum sub product, it is characterized in that said coal is brown coal or young bituminous coal; Said promotor is a sulphur; Said oil is the low-quality oil or the heavy oil of high metal content, high asphalt content; Said refining of petroleum sub product is extraction aromatic hydrocarbons, the extraction aromatic hydrocarbons of wax tailings or the extraction aromatic fraction oil of lubricating oil aromatic extraction unit of externally extracting oil of extraction aromatic hydrocarbons, CCU of heavy cycle oil of externally extracting oil, the CCU of heavy recycle stock, clarified oil, CCU in the CCU.
3. according to the coal direct liquefaction method with oil or the alternative circulating solvent of refining of petroleum sub product of claim 1, it is characterized in that said refining of petroleum sub product is heavy recycle stock, clarified oil or the externally extracting oil in the CCU.
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