CN104910962A - Direct-coal-liquefied circulating hydrogen-donor solvent and preparation method thereof - Google Patents
Direct-coal-liquefied circulating hydrogen-donor solvent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a direct-coal-liquefied circulating hydrogen-donor solvent and a preparation method thereof. The preparation method comprises the following steps: (S1) carrying out catalytic hydrogenation on a direct-coal-liquefied effluent so as to obtain a gas-phase product and a liquid-phase product; (S2) carrying out fractional distillation on the liquid-phase product so as to obtain a light oil fraction and a heavy oil fraction; (S3) carrying out solvent extraction on the heavy oil fraction so as to obtain rich-aromatic-hydrocarbon oil and lean-aromatic-hydrocarbon oil, and taking the rich-aromatic-hydrocarbon oil as the direct-coal-liquefied circulating hydrogen-donor solvent, wherein the distillation range of the light oil fraction is equal to or lower than 200 DEG C, and the distillation range of the heavy oil fraction is higher than 200 DEG C. Due to the catalytic hydrogenation and fractional distillation process for the direct-coal-liquefied effluent, the content of partially-saturated aromatic hydrocarbons in the heavy oil fraction can be integrally increased; the heavy oil fraction is subjected to solvent extraction, so that the removal of saturated components without or with relatively low hydrogen supplying capacity is facilitated, the circulating hydrogen-donor solvent with relatively high hydrogen supplying capacity is obtained, and then the conversion rate of coal and yield of oil in a coal liquefaction process are increased.
Description
Technical field
The present invention relates to direct coal liquefaction process technical field, in particular to a kind of DCL/Direct coal liquefaction circulation hydrogen supply dissolvent and preparation method thereof.
Background technology
DCL/Direct coal liquefaction refer to High Temperature High Pressure, face hydrogen, solvent and catalyzer effect under, coal is carried out hydrocracking, generates the technological process of liquid product.Solvent is the important medium of Coal liquefaction process, and its Main Function comprises: solvent and coal are made into coal slurry, is convenient to conveying and the pressurization of coal; Coal can dissolve by solvent, and the free radical fragment polycondensation preventing pyrolysis of coal from producing, thus improve the yield of liquefied coal coil; Solvent can dissolve gas phase hydrogen, makes hydrogen molecule to coal or catalyst surface diffusion; Solvent to the direct hydrogen supply of free radical fragment or can also transmit hydrogen.Therefore DCL/Direct coal liquefaction solvent should have stronger dissolving power to the free radical fragment of pyrolysis of coal, also will possess good hydrogen supply capacity simultaneously.
Since direct coal liquefaction technology exploitation, the proposition of hydrogen supply dissolvent and application make direct coal liquefaction technology obtain breakthrough development.Due to quoting of hydrogen supply dissolvent, DCL/Direct coal liquefaction operational condition reduces greatly, and as working pressure is down to 15 ~ 20MPa, temperature of reaction is down to 430 ~ 460 DEG C.Modern typical direct coal liquefaction process, the Shenhua direct coal liquefaction process etc. of Exxon hydrogen supply dissolvent (EDS) technique of such as USP4046054, the catalysis of USP4842719 two sections of gelatin liquefaction CTSL techniques, Japanese NEDOL technique and CN15873518A, in normal operation, DCL/Direct coal liquefaction solvent all reacts from DCL/Direct coal liquefaction.After solvent hydrogenation, for coal slurry preparation, and recycle in DCL/Direct coal liquefaction process, be referred to as gelatin liquefaction circulation hydrogen supply dissolvent.Solvent hydrogen supply capacity can promote the conversion of coal, thus add the yield of coal direct liquefaction oil after improving.In the real-world operation of small-sized long run test device (BSU), process exploitation apparatus (PDU) and megaton Firing Shenhua Coal direct liquefaction demonstration unit (DP), the solvent that hydrogen supply capacity is good, not only directly affects the transformation efficiency of coal and the yield of coal direct liquefaction oil, also help the preparation of coal slurry, conveying and mobility etc.
There are some researches show, partially hydrogenated polycyclic aromatic hydrocarbons (as naphthane, dihydro phenanthrene, dihydroanthracene, tetrahydrochysene anthracene) has very strong hydrogen supply capacity, and stable hydrocarbon does not possess or has very weak hydrogen supply capacity.The hydrogen supply capacity research of current circulating solvent has become one of emphasis of direct coal liquefaction technology research field, the raising of solvent hydrogen supply capacity is conducive to improving the transformation efficiency of coal and the yield of coal direct liquefaction oil, and the solvent of the hydrogen supply capacity or exploitation excellent property that therefore improve circulating solvent is further an important directions of direct coal liquefaction technology development.
Chinese patent application CN101370914 discloses a kind of method of hydrotreating of brown coal directly liquefied circulating solvent, and principal feature is the incomplete saturated hydrogenation realizing coal liquefaction solvent under the processing condition relaxed, and improves the confession hydrogen amount of solvent.In the direct coal liquefaction process of Chinese patent application CN1587351A, liquefied coal coil, after stabilized hydrogenation, removes most of sulphur, nitrogen and nitrogen heteroatom, and prior to carry out partial hydrogenation to aromatic hydrocarbons saturated, improves the hydrogen supply capacity of circulating solvent.But owing to containing fractional saturation hydrocarbon in the liquefied coal coil that DCL/Direct coal liquefaction is produced, after hydrotreatment, saturated hydrocarbon content improves further, account for circulation hydrogen supply dissolvent about 30%, this part stable hydrocarbon does not have or has very weak hydrogen supply capacity in DCL/Direct coal liquefaction process, thus have impact on the transformation efficiency of coal and oily yield.
Known by foregoing, the stable hydrocarbon containing high level in the circulation hydrogen supply dissolvent adopting existing technique to obtain, this causes the hydrogen supply capacity of the circulation hydrogen supply dissolvent obtained poor.In order to address this problem, be necessary to develop a kind of method preparing high hydrogen supply capacity circulation hydrogen supply dissolvent.
Summary of the invention
The present invention aims to provide a kind of DCL/Direct coal liquefaction circulating solvent and preparation method thereof, to solve the poor defect of the circulation hydrogen supply dissolvent hydrogen supply capacity that utilizes prior art to obtain.
To achieve these goals, one aspect of the invention provides a kind of preparation method of DCL/Direct coal liquefaction circulation hydrogen supply dissolvent, comprises the following steps: S1, coal direct liquefaction oil is carried out shortening, obtain gas-phase product and liquid product; S2, carries out fractionation by liquid product, obtains light ends oil and heavy distillate; S3, carries out solvent extraction by heavy distillate, obtains rich aromatic hydrocarbon oil and poor aromatic hydrocarbon oil, to be circulated hydrogen supply dissolvent by rich aromatic hydrocarbon oil as DCL/Direct coal liquefaction; Wherein, light ends oil is less than or equal to the distillate of 200 DEG C for boiling range, and heavy distillate is the distillate that boiling range is greater than 200 DEG C.
Further, heavy distillate is the distillate that boiling range is greater than 220 DEG C.
Further, in solvent extraction process, the extraction solvent of employing is density >0.95cm
3the organic solvent of/g, boiling point <210 DEG C; Preferably, extraction solvent is selected from one or more in the group of furfural, N-Methyl pyrrolidone and dimethyl sulfoxide (DMSO) composition.
Further, in solvent extraction process, extraction temperature is 30 ~ 100 DEG C, and solvent ratio is 0.5 ~ 3.5.
Further, the coal direct liquefaction oil DCL/Direct coal liquefaction distillate that is DCL/Direct coal liquefaction full distillate oil or is greater than 180 DEG C for boiling range; Preferably, coal direct liquefaction oil is the DCL/Direct coal liquefaction distillate of boiling range 200 ~ 480 DEG C.
Further, in catalytic hydrogenation, catalyst active component is the base metal of VIB and/or VIII; Preferred catalytic agent carrier is amorphous oxide or silicate.
Further, the base metal of group vib is Mo and/or W, and the base metal of VIII is Co and/or Ni; Preferred catalytic agent carrier is amorphous alumina or pure aluminium silicate.
Further, in catalytic hydrogenation, the hydrogenator of employing is fixed-bed reactor, expanded bed reactor or pressure internal recycle ebullated bed reactor; Alternatively, in solvent extraction process, the extraction plant of employing is tray column or rotating disc contactor.
Further, in step S3, using poor aromatic hydrocarbon oil and light ends oil as Coal Liquefaction Products.
The present invention additionally provides a kind of circulation hydrogen supply dissolvent on the other hand, adopts above-mentioned preparation method to obtain.
The present invention aims to provide a kind of DCL/Direct coal liquefaction circulation hydrogen supply dissolvent and preparation method thereof.Apply technical scheme of the present invention, catalytic hydrogenation and fractionation process can the content of fractional saturation aromatic hydrocarbons in Integral lifting heavy distillate, meanwhile, can also reduce the viscosity of circulating solvent, and then reduce the viscosity of coal oil mixture in later stage coal liquefaction, improve transportability.Heavy distillate is carried out solvent extraction, be conducive to removing that not there is hydrogen supply capacity or that hydrogen supply capacity is more weak saturated component, in the rich aromatic hydrocarbon oil obtained, saturated component concentration is less, as during circulation hydrogen supply dissolvent, there is higher hydrogen supply capacity, thus be conducive to improving the coal transformation efficiency in coal liquefaction and oily yield.Simultaneously, because solvent extraction improves the content of aromatic hydrocarbons in circulation hydrogen supply dissolvent, according to the similar principle that mixes, circulation hydrogen supply dissolvent is effectively promoted the dissolving of coal and pyrolysis of coal free radical and dispersive ability, and polycyclic aromatic hydrocarbon content increase also can improve solvent hydrogen transference ability, thus be conducive to improving the transformation efficiency of coal in DCL/Direct coal liquefaction process and the yield of oil further.
Accompanying drawing explanation
The Figure of description forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
The schematic diagram of the process system that the preparation method that Fig. 1 shows DCL/Direct coal liquefaction circulating solvent in the embodiment of the present invention adopts.
Reference numeral in Fig. 1 is as follows:
110, raw materials furnace and heating; 120, hydrogenator; 130, high pressure hot separator; 140, cold high pressure separator; 150, process furnace; 160, separation column; 170, extraction plant; 180, regenerator column; 190, vacuum distillation tower; 101, refrigerating unit; 102, circulating hydrogen compressor.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.The present invention is described in detail below in conjunction with embodiment.
As described by background technology part, stable hydrocarbon containing high level in the circulation hydrogen supply dissolvent adopting existing technique to obtain, this causes the hydrogen supply capacity of the circulation hydrogen supply dissolvent obtained poor, and then the transformation efficiency that have impact in DCL/Direct coal liquefaction process and oily yield.In order to address this problem, the invention provides a kind of preparation method of DCL/Direct coal liquefaction circulation hydrogen supply dissolvent, comprising the following steps: S1, coal direct liquefaction oil is carried out shortening, obtain gas-phase product and liquid product; S2, carries out fractionation by liquid product, obtains light ends oil and heavy distillate; S3, carries out solvent extraction by heavy distillate, obtains rich aromatic hydrocarbon oil and poor aromatic hydrocarbon oil, to be circulated hydrogen supply dissolvent by rich aromatic hydrocarbon oil as DCL/Direct coal liquefaction; Wherein, light ends oil refers to that boiling range is less than or equal to the distillate of 200 DEG C, and heavy distillate refers to that boiling range is greater than the distillate of 200 DEG C.
Above-mentioned " liquid product " can be the liquid product directly obtained in catalytic hydrogenation; Also following two portions can be comprised: wherein a part is the liquid product directly obtained in catalytic hydrogenation, and another part is the liquid product that the gas phase directly obtained in catalytic hydrogenation is formed after partial condensation.
In above-mentioned preparation method provided by the present invention, catalytic hydrogenation and fractionation process can the content of fractional saturation aromatic hydrocarbons in Integral lifting heavy distillate, meanwhile, can also reduce the viscosity of circulating solvent, and then reduce the viscosity of coal oil mixture in later stage coal liquefaction, improve transportability.Heavy distillate is carried out solvent extraction, be conducive to removing that not there is hydrogen supply capacity or that hydrogen supply capacity is more weak saturated component, in the rich aromatic hydrocarbon oil obtained, saturated component concentration is less, as during circulation hydrogen supply dissolvent, there is higher hydrogen supply capacity, thus be conducive to improving the coal transformation efficiency in coal liquefaction and oily yield.Simultaneously, because solvent extraction improves the content of aromatic hydrocarbons in circulation hydrogen supply dissolvent, according to the similar principle that mixes, circulation hydrogen supply dissolvent is effectively promoted the dissolving of coal and pyrolysis of coal free radical and dispersive ability, and polycyclic aromatic hydrocarbon content increase also can improve solvent hydrogen transference ability, thus be conducive to improving the transformation efficiency of coal in DCL/Direct coal liquefaction process and the yield of oil further.
In above-mentioned preparation method, as long as carry out fractionation according to the boiling range of above-mentioned light ends oil and heavy distillate, in the heavy distillate obtained, the content of fractional saturation aromatic hydrocarbons is namely relatively high.In a preferred embodiment, heavy distillate is the distillate that boiling range is greater than 220 DEG C.This is conducive to being separated the hydrogen donor component in coal direct liquefaction oil hydrogenation products and non-hydrogen donor component (or weak hydrogen donor component) more fully, make the aromatic hydrocarbons in final DCL/Direct coal liquefaction circulation hydrogen supply dissolvent with more high-content, thus possess higher hydrogen supply capacity.
In preparation method provided by the present invention, as long as the solvent adopted in solvent extraction process can by aromatic hydrocarbons extraction out.In a preferred embodiment, in solvent extraction process, the extraction solvent of employing is density >0.95cm
3the organic solvent of/g, boiling point <200 DEG C.This kind of solvent stability is good, higher to the selectivity of aromatic hydrocarbons, and poor to stable hydrocarbon selectivity.This is conducive to the effect of extracting improving aromatic hydrocarbons further, to improve the hydrogen supply capacity of circulation hydrogen supply dissolvent further.More preferably, extraction solvent includes but not limited to furfural, N-Methyl pyrrolidone or dimethyl sulfoxide (DMSO).
According to instruction of the present invention, those skilled in the art can concrete technology condition in selective solvent extraction process.In a preferred embodiment, in solvent extraction process, extraction temperature is 30 ~ 100 DEG C, and solvent ratio is 0.5 ~ 3.5." solvent ratio " that the present invention relates to refers to the weight ratio of distillate to be extracted and extraction solvent.Extraction temperature is controlled in above-mentioned scope, and the amount ratio of distillate to be extracted and extraction solvent is controlled in above-mentioned scope, be conducive to improving effect of extracting, the aromatic hydrocarbons in distillate to be extracted is separated more fully.Above-mentioned solvent extraction refers to the solvent extraction process that those skilled in the art of the present technique are familiar with.Extraction plant can be the usual extraction plant in this area, and preferably, this extraction plant includes but not limited to use tray column and rotating disc contactor.This returns extraction plant, recycles after being conducive to extraction solvent regeneration purification.
In preparation method provided by the present invention, the raw material adopted in the shortening stage is coal direct liquefaction oil.In a preferred embodiment, the DCL/Direct coal liquefaction distillate that the raw material adopted in the shortening stage is DCL/Direct coal liquefaction full distillate oil or is greater than 180 DEG C for boiling range.Namely the hydrogen supply dissolvent obtained by above-mentioned raw materials has good hydrogen supply capacity.
In preparation method provided by the present invention, the raw material adopted in the shortening stage is that DCL/Direct coal liquefaction full distillate oil or the DCL/Direct coal liquefaction distillate that is greater than 180 DEG C for boiling range can obtain hydrogen supply hydrogen supply dissolvent of good performance.In a preferred embodiment, the raw material adopted in the shortening stage is the DCL/Direct coal liquefaction distillate of boiling range 200 ~ 480 DEG C.In the DCL/Direct coal liquefaction distillate of boiling range 200 ~ 480 DEG C, the content of the unsaturated aromatic hydrocarbon contained is higher.After later stage shortening, fractionation and solvent extraction, the hydrogen supply capacity of the DCL/Direct coal liquefaction circulation hydrogen supply dissolvent obtained enhances by force further.
In preparation method provided by the present invention, those skilled in the art can concrete technology condition in selective catalysis hydrogenation process.In a preferred embodiment, catalytic hydrogenation reaction condition is: temperature of reaction 280 ~ 400 DEG C, reaction pressure 5 ~ 20MPa, hydrogen-oil ratio 300 ~ 1200, volume space velocity 0.5 ~ 3.0h
-1.This is conducive to the carrying out of catalytic hydrogenation reaction, improves the content of fractional saturation aromatic hydrocarbons in hydrogenation reaction, thus increases the content of active hydrogen, to improve the hydrogen supply capacity of circulation hydrogen supply dissolvent further.
In preparation method provided by the present invention, the catalyzer that catalytic hydrogenation adopts those skilled in the art conventional in coal direct liquefaction oil hydrogenation process.In a preferred embodiment, in catalytic hydrogenation, catalyst active component includes but not limited to the base metal of VIB and/or VIII.Such catalyzer has good hydrotreated lube base oil activity and hydrodenitrogenationactivity activity, be conducive to the carrying out of catalytic hydrogenation reaction, improve the growing amount of fractional saturation aromatic hydrocarbons in hydrogenation reaction, increase the content of active hydrogen, and then improve the hydrogen supply capacity of circulation hydrogen supply dissolvent.Preferably, support of the catalyst includes but not limited to amorphous oxide or silicate.More preferably, the base metal of group vib is Mo and/or W, and the base metal of VIII is Co and/or Ni; Support of the catalyst is amorphous alumina or pure aluminium silicate.
In preparation method provided by the present invention, the reactor that catalytic hydrogenation adopts those skilled in the art to commonly use.In a preferred embodiment, in catalytic hydrogenation, the hydrogenator of employing includes but not limited to fixed-bed reactor, expanded bed reactor or forces internal recycle ebullated bed reactor.Adopt above-mentioned several hydrogenator can avoid the generation of side reaction in catalytic hydrogenation reaction, avoid the situation of hydrogenation supersaturation and hydrogenation depth deficiency simultaneously.Preferably, the hydrogenator of employing is for forcing internal recycle ebullated bed reactor.
In preparation method provided by the present invention, as long as just can obtain having according to above-mentioned technique and parameter the DCL/Direct coal liquefaction circulation hydrogen supply dissolvent that higher part divides saturated aromaticity content.In a preferred embodiment, in described step S3, using poor aromatic hydrocarbon oil and light ends oil as Coal Liquefaction Products.Heavy distillate is after solvent extraction, in the poor aromatic hydrocarbon oil obtained, the content of aromatic hydrocarbons significantly reduces, using its together with light ends oil as Coal Liquefaction Products time, be conducive to the difficulty reducing Coal Liquefaction Products further hydro-upgrading, thus improve the quality of final upgraded products.
The present invention additionally provides a kind of circulation hydrogen supply dissolvent on the other hand, adopts above-mentioned preparation method to obtain.
Circulation hydrogen supply dissolvent provided by the present invention has the fractional saturation aromatic hydrocarbons of high level, during as circulation hydrogen supply dissolvent, has higher hydrogen supply capacity, thus is conducive to improving the coal transformation efficiency in coal liquefaction and oily yield.Meanwhile, compared to existing circulation hydrogen supply dissolvent, this circulation hydrogen supply dissolvent is to the dissolving of coal and pyrolysis of coal free radical and dispersive ability, and hydrogen transference ability is all better.
Be described in further detail the present invention below in conjunction with specific embodiment, these embodiments can not be interpreted as restriction the present invention scope required for protection.
In following examples 1 to 4 and comparative example 1 respectively with the full distillate oil of coal direct liquefaction oil or boiling range be greater than 180 DEG C or boiling range be the distillate of 200 ~ 480 DEG C for stock oil, carry out the preparation of DCL/Direct coal liquefaction circulation hydrogen supply dissolvent.The character of this coal direct liquefaction oil is shown in Table 1:
The character of table 1 coal direct liquefaction oil
| Density (20 DEG C) | 0.9592g/cm 3 |
| Boiling range (ASTM D86)/DEG C | Per-cent % |
| 177/219.7 | IBP/5％ |
| 230.7/260.4 | 10％/30％ |
| 295.5/341.4 | 50％/70％ |
| 431.7/431.8 | 90％/FBP |
Embodiment 1
As shown in Figure 1, DCL/Direct coal liquefaction full distillate oil is introduced in stock oil surge tank, mix with hydrogen after the boosting of high pressure feedstock pump, incoming stock process furnace 110.Heat temperature raising, the gas-oil mixture after being heated enters hydrogenator 120 (expanded bed reactor), at 300 DEG C, carry out hydrogenation reaction in reactor, to make aromatic moiety saturated, carries out heteroatoms simultaneously and removes reaction.The carrier that the catalyzer of catalytic hydrogenation reaction adopts is aluminum oxide, and activeconstituents is Mo, Co and Ni.
Hydrogenator 120 outlet material enters high pressure hot separator 130 after heat exchange cooling, and the temperature of high pressure hot separator 130 controls at 250 DEG C.High pressure hot separator 130 gas phase out enters cold high pressure separator 140 after apparatus for supercooling 101 cools, and cold high pressure separator 140 temperature controls below 54 DEG C.Cold high pressure separator 140 gas phase portion out, after circulating hydrogen compressor 102 boosts, is circulated to raw materials furnace and heating 110 entrance, and part is discharged.The liquid phase part of high pressure hot separator 130, after decompression, mixes with the liquid phase part of cold high pressure separator 140, then enters fractionation charging process furnace 150.Fractionation raw material enters separation column 160 and carries out fractionation after the heating of fractionation charging process furnace 150, boiling range is greater than the distillate of 200 DEG C as heavy distillate, meanwhile, boiling range is less than or equal to the cut of 200 DEG C as light ends oil.
Heavy distillate enters extraction plant 170 (tray column), and extraction solvent alditol is entered by extraction plant 170 tower top, and at the bottom of extraction plant 170 tower, extraction phase enters vacuum distillation tower 190, is 0.4 carry out solvent extraction at 30 DEG C with solvent ratio.The rich aromatic hydrocarbon oil of output at the bottom of vacuum distillation tower 190 tower to circulate hydrogen supply dissolvent as DCL/Direct coal liquefaction.
The extraction solvent of vacuum distillation tower 190 tower top enters extraction solvent regenerator column 180, uses through regeneration Posterior circle.The extracting phase of extraction plant 170 tower top is poor aromatic hydrocarbon oil, and the light ends oil of this poor aromatic hydrocarbon oil and separation column 160 tower top output is mixed into Coal Liquefaction Products, after downstream hydrogenation upgrading, can produce vehicle fuel.
Embodiment 2
As shown in Figure 1, DCL/Direct coal liquefaction full distillate oil is introduced in stock oil surge tank, mix with hydrogen after the boosting of high pressure feedstock pump, incoming stock process furnace 110.Heat temperature raising, the gas-oil mixture after being heated enters hydrogenator 120 (expanded bed reactor), at 320 DEG C, carry out hydrogenation reaction in reactor, to make aromatic moiety saturated, carries out heteroatoms simultaneously and removes reaction.The carrier that the catalyzer of catalytic hydrogenation reaction adopts is pure aluminium silicate, and activeconstituents is Mo, Co and Ni.
Hydrogenator 120 outlet material enters high pressure hot separator 130 after heat exchange cooling, and the temperature of high pressure hot separator 130 controls at 250 DEG C.High pressure hot separator 130 gas phase out enters cold high pressure separator 140 after apparatus for supercooling 101 cools, and cold high pressure separator 140 temperature controls below 54 DEG C.Cold high pressure separator 140 gas phase portion out, after circulating hydrogen compressor 102 boosts, is circulated to raw materials furnace and heating 110 entrance, and part is discharged.The liquid phase part of high pressure hot separator 130, after decompression, mixes with the liquid phase part of cold high pressure separator 140, then enters fractionation charging process furnace 150.Fractionation raw material enters separation column 160 and carries out fractionation after the heating of fractionation charging process furnace 150, boiling range is greater than the distillate of 200 DEG C as heavy distillate, meanwhile, boiling range is less than or equal to the cut of 200 DEG C as light ends oil.
Heavy distillate enters extraction plant 170 (tray column), and extraction solvent alditol is entered by extraction plant 170 tower top, and at the bottom of extraction plant 170 tower, extraction phase enters vacuum distillation tower 190, is 3.5 carry out solvent extraction at 30 DEG C with solvent ratio.The rich aromatic hydrocarbon oil of output at the bottom of vacuum distillation tower 190 tower to circulate hydrogen supply dissolvent as DCL/Direct coal liquefaction.
The extraction solvent of vacuum distillation tower 190 tower top enters extraction solvent regenerator column 180, uses through regeneration Posterior circle.The extracting phase of extraction plant 170 tower top is poor aromatic hydrocarbon oil, and the light ends oil of this poor aromatic hydrocarbon oil and separation column 160 tower top output is mixed into Coal Liquefaction Products, after downstream hydrogenation upgrading, can produce vehicle fuel.
Embodiment 3
As shown in Figure 1, be greater than DCL/Direct coal liquefaction boiling range in the distillate introducing stock oil surge tank of 180 DEG C, mix with hydrogen after the boosting of high pressure feedstock pump, incoming stock process furnace 110.Heat temperature raising, the gas-oil mixture after being heated enters hydrogenator 120 (fixed-bed reactor), carries out catalytic hydrogenation reaction and satisfies to make aromatic moiety, carry out heteroatoms simultaneously and remove reaction at 390 DEG C in reactor.The carrier that the catalyzer of catalytic hydrogenation reaction adopts is pure aluminium silicate, and activeconstituents is W, Co and Ni.
Hydrogenator 120 outlet material enters high pressure hot separator 130 after heat exchange cooling, and the temperature of high pressure hot separator 130 controls at 250 DEG C.High pressure hot separator 130 gas phase out enters cold high pressure separator 140 after apparatus for supercooling 101 cools, and cold high pressure separator 140 temperature controls below 54 DEG C.Cold high pressure separator 140 gas phase portion out, after circulating hydrogen compressor 102 boosts, is circulated to raw materials furnace and heating 110 entrance, and part is discharged.The liquid phase part of high pressure hot separator 130, after decompression, mixes with the liquid phase part of cold high pressure separator 140, then enters fractionation charging process furnace 150.Fractionation raw material enters separation column 160 and carries out fractionation after the heating of fractionation charging process furnace 150, boiling range is greater than the distillate of 220 DEG C as heavy distillate, meanwhile, boiling range is less than or equal to the cut of 220 DEG C as light ends oil.
Heavy distillate enters extraction plant 170 (rotating disc contactor), and extraction solvent dimethyl sulfoxide (DMSO) is entered by extraction plant 170 tower top, is 0.5 carry out solvent extraction at 100 DEG C with solvent ratio.At the bottom of extraction plant 170 tower, extraction phase enters vacuum distillation tower 190.Rich aromatic hydrocarbon oil at the bottom of vacuum distillation tower 190 tower mixes as DCL/Direct coal liquefaction circulation hydrogen supply dissolvent with the heavy distillate at separation column 160 end.
The extraction solvent of vacuum distillation tower 190 tower top enters extraction solvent regenerator column 180, uses through regeneration Posterior circle.The extracting phase of extraction plant 170 tower top is poor aromatic hydrocarbon oil, and the light ends oil of this poor aromatic hydrocarbon oil and separation column 160 tower top output is mixed into Coal Liquefaction Products, after downstream hydrogenation upgrading, can produce vehicle fuel.
Embodiment 4
As shown in Figure 1, be that the distillate of 200 ~ 480 DEG C is introduced in stock oil surge tank by DCL/Direct coal liquefaction boiling range, its essential property, in table 2, mixes with hydrogen, incoming stock process furnace 110 after the boosting of high pressure feedstock pump.Heat temperature raising, the gas-oil mixture after being heated enters hydrogenator 120 (forcing internal recycle ebullated bed reactor), carries out hydrogenation reaction and satisfies to make aromatic moiety, carry out heteroatoms simultaneously and remove reaction at 375 DEG C.The carrier that the catalyzer of catalytic hydrogenation reaction adopts is pure aluminium silicate, and activeconstituents is Mo and Ni.
Hydrogenator 120 outlet material enters high pressure hot separator 130 after heat exchange cooling, and the temperature of high pressure hot separator 130 controls at 250 DEG C.High pressure hot separator 130 gas phase out enters cold high pressure separator 140 after apparatus for supercooling 101 cools, and cold high pressure separator 140 temperature controls below 54 DEG C.Cold high pressure separator 140 gas phase portion out, after circulating hydrogen compressor 102 boosts, is circulated to raw materials furnace and heating 110 entrance, and part is discharged.The liquid phase part of high pressure hot separator 130, after decompression, mixes with the liquid phase part of cold high pressure separator 140, then enters fractionation charging process furnace 150.Fractionation raw material enters separation column 160 after the heating of fractionation charging process furnace 150, carries out fractionation, boiling range is greater than the distillate of 220 DEG C as heavy distillate, meanwhile, boiling range is less than or equal to the distillate of 220 DEG C as light ends oil.
Heavy distillate is passed into extraction plant 170 (rotating disc contactor), extraction solvent N-Methyl pyrrolidone is entered by extraction plant 170 tower top, is 3 carry out solvent extraction at 100 DEG C with solvent ratio.At the bottom of extraction plant 170 tower, extraction phase enters vacuum distillation tower 190.At the bottom of vacuum distillation tower 190 tower, the rich aromatic hydrocarbon oil of output mixes as DCL/Direct coal liquefaction circulation hydrogen supply dissolvent with the heavy distillate of separation column 160 end output.
The extraction solvent of vacuum distillation tower 190 tower top enters extraction solvent regenerator column 180, uses through regeneration Posterior circle.The extracting phase of extraction plant 170 (rotating disc contactor) tower top is poor aromatic hydrocarbon oil, and the light ends oil of poor aromatic hydrocarbon oil and separation column 160 tower top output is mixed into Coal Liquefaction Products, after downstream hydrogenation upgrading, can produce vehicle fuel.
Comparative example 1
As shown in Figure 1, DCL/Direct coal liquefaction full distillate oil is introduced in stock oil surge tank, mix with hydrogen after the boosting of high pressure feedstock pump, incoming stock process furnace 110.Heat temperature raising, the gas-oil mixture after being heated enters hydrogenator 120 (expanded bed reactor), at 375 DEG C, carry out hydrogenation reaction in reactor, to make aromatic moiety saturated, carries out heteroatoms simultaneously and removes reaction.The carrier that the catalyzer of catalytic hydrogenation reaction adopts is aluminum oxide, and activeconstituents is Mo, Co and Ni.
Hydrogenator 120 outlet material enters high pressure hot separator 130 after heat exchange cooling, and the temperature of high pressure hot separator 130 controls at 250 DEG C.High pressure hot separator 130 gas phase out enters cold high pressure separator 140 after apparatus for supercooling 101 cools, and cold high pressure separator 140 temperature controls below 54 DEG C.Cold high pressure separator 140 gas phase portion out, after circulating hydrogen compressor 102 boosts, is circulated to raw materials furnace and heating 110 entrance, and part is discharged.The liquid phase part of high pressure hot separator 130, after decompression, mixes with the liquid phase part of cold high pressure separator 140, then enters fractionation charging process furnace 150.Fractionation raw material enters separation column 160 and carries out fractionation after the heating of fractionation charging process furnace 150, boiling range is greater than the distillate of 200 DEG C as heavy distillate, meanwhile, boiling range is less than or equal to the cut of 200 DEG C as light ends oil.
Using the heavy distillate of separation column 160 tower bottom output as circulation hydrogen supply dissolvent, the light ends oil of separation column 160 tower top output, as Coal Liquefaction Products, after downstream hydrogenation upgrading, can produce vehicle fuel.
In the present invention, " solvent ratio " all refers to the weight ratio of distillate to be extracted and extraction solvent.
Reaction conditions in embodiment 1 to 4 is compared, and circulating solvent obtained in embodiment 1 to 4 and comparative example 1 is applied in DCL/Direct coal liquefaction reaction, its coal transformation efficiency is compared:
In embodiment 1 to 4 and comparative example 1, the catalyzer of catalytic hydrogenation reaction is in table 3;
In embodiment 1 to 4 and comparative example 1, catalytic hydrogenation reaction condition is in table 4;
In embodiment 1 to 4 and comparative example 1, the character of circulating solvent is in table 5.
Table 3
Table 4
Table 5
| Hydrocarbon composition/wt% | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 |
| Paraffinic hydrocarbons | 3.2 | 0.4 | 3.1 | 0.5 | 4.8 |
| One naphthenic hydrocarbon | 8.5 | 4.3 | 9.6 | 4.6 | 11.9 |
| Bicyclic alkane | 6.1 | 3.8 | 6.4 | 4.1 | 7.8 |
| Three naphthenic hydrocarbon | 5.2 | 2.5 | 5.8 | 3.2 | 6.2 |
| Fourth Ring alkane | 1.4 | 1.3 | 1.3 | 1.2 | 1.9 |
| Total naphthenic hydrocarbon | 21.2 | 11.9 | 23.1 | 13.1 | 27.8 |
| Total stable hydrocarbon | 25.4 | 12.3 | 26.2 | 13.6 | 32.6 |
| Alkylbenzene | 3.8 | 5.2 | 5.6 | 5.8 | 5.4 |
| Cycloalkyl benzene | 21.8 | 28.4 | 28.9 | 34.8 | 25.9 |
| Bicyclic alkyl benzene | 14.7 | 17.6 | 20.8 | 24.7 | 19.2 |
| Total mononuclear aromatics | 50.2 | 51.2 | 55.3 | 65.3 | 50.5 |
| Naphthalene class | 5.3 | 6.4 | 5.5 | 6.2 | 4.8 |
| Acenaphthene class+diphenylene-oxide | 8.2 | 8.9 | 4.5 | 5.5 | 4.2 |
| Fluorenes class | 6.4 | 7.1 | 3.2 | 3.8 | 2.9 |
| Total double ring arene | 16 | 22.4 | 13.2 | 15.5 | 11.9 |
| Thrcylic aromatic hydrocarbon | 4.2 | 8.5 | 2.8 | 3.2 | 2.5 |
| Four Polycyclic aromatic hydrocarbons | 3.1 | 5.1 | 1.5 | 1.7 | 1.3 |
| Total aromatic hydrocarbons | 73.5 | 87.2 | 72.8 | 85.7 | 66.2 |
Coal transformation efficiency is tested:
Adopt the circulation hydrogen supply dissolvent of preparation in embodiment 1 to 4 and comparative example 1, in the autoclave of 0.5L, investigate its DCL/Direct coal liquefaction reactivity worth.Analysis of coal sample data used, in table 6; DCL/Direct coal liquefaction rate test result, in table 7.
Table 6
Table 7
From above data, the above embodiment of the present invention achieves following beneficial effect: the mixing oil of embodiment 1 to 4 centering matter distillate and heavy distillate has carried out solvent extraction process, comparative example 1 does not carry out solvent extraction process, and other is identical with embodiment 1.As can be seen from Table 7, adopt circulation hydrogen supply dissolvent prepared by the present invention, after solvent extraction, the transformation efficiency of coal increases to 88.90% by the 87.95wt% not carrying out solvent extraction process; Oil yield increases to 59.52wt% by 55.57wt%.In the present invention, coal direct liquefaction oil, after hydrotreatment, makes polycyclic aromatic hydrocarbons fractional saturation, removes the stable hydrocarbon in DCL/Direct coal liquefaction circulating solvent without hydrogen supply capacity simultaneously; Improve the aromaticity content of circulating solvent, reduce saturated hydrocarbon content, reach the object improving circulation hydrogen supply dissolvent hydrogen supply capacity, thus improve the transformation efficiency of coal and oily yield.
In above-mentioned preparation method provided by the present invention, catalytic hydrogenation and fractionation process can the content of fractional saturation aromatic hydrocarbons in Integral lifting heavy distillate, meanwhile, can also reduce the viscosity of circulating solvent, and then reduce the viscosity of coal oil mixture in later stage coal liquefaction, improve transportability.
Heavy distillate is carried out solvent extraction, be conducive to removing that not there is hydrogen supply capacity or that hydrogen supply capacity is more weak saturated component, in the rich aromatic hydrocarbon oil obtained, saturated component concentration is less, as during circulation hydrogen supply dissolvent, there is higher hydrogen supply capacity, thus be conducive to improving the coal transformation efficiency in coal liquefaction and oily yield.Simultaneously, because solvent extraction improves the content of aromatic hydrocarbons in circulation hydrogen supply dissolvent, according to the similar principle that mixes, circulation hydrogen supply dissolvent is effectively promoted the dissolving of coal and pyrolysis of coal free radical and dispersive ability, and polycyclic aromatic hydrocarbon content increase also can improve solvent hydrogen transference ability, thus be conducive to improving the transformation efficiency of coal in DCL/Direct coal liquefaction process and the yield of oil further.
Heavy distillate is after solvent extraction, in the poor aromatic hydrocarbon oil obtained, the content of aromatic hydrocarbons significantly reduces, using its together with light ends oil as Coal Liquefaction Products time, be conducive to the difficulty reducing Coal Liquefaction Products further hydro-upgrading, thus improve the quality of final upgraded products.
In addition, the technique of preparation circulation hydrogenation solvent provided by the invention, its catalytic hydrogenation technical maturity, flexibly, reliable; Reaction unit is strong to adaptability to raw material, and the Nature comparison of hydrogenated oil is stablized; Aromatic hydrocarbons takes out the technique that technological process also has maturation simultaneously, is convenient to realize.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for DCL/Direct coal liquefaction circulation hydrogen supply dissolvent, is characterized in that, comprises the following steps:
S1, carries out shortening by coal direct liquefaction oil, obtains gas-phase product and liquid product;
S2, carries out fractionation by described liquid product, obtains light ends oil and heavy distillate;
S3, carries out solvent extraction by described heavy distillate, obtains rich aromatic hydrocarbon oil and poor aromatic hydrocarbon oil, using described rich aromatic hydrocarbon oil as described DCL/Direct coal liquefaction circulation hydrogen supply dissolvent;
Wherein, described light ends oil is less than or equal to the distillate of 200 DEG C for boiling range, and described heavy distillate is the distillate that boiling range is greater than 200 DEG C.
2. preparation method according to claim 1, is characterized in that, described heavy distillate is the distillate that boiling range is greater than 220 DEG C.
3. preparation method according to claim 1 and 2, is characterized in that, in described solvent extraction process, the extraction solvent of employing is density >0.95cm
3the organic solvent of/g, boiling point <210 DEG C; Preferably, described extraction solvent is selected from one or more in the group of furfural, N-Methyl pyrrolidone and dimethyl sulfoxide (DMSO) composition.
4. preparation method according to claim 3, is characterized in that, in described solvent extraction process, extraction temperature is 30 ~ 100 DEG C, and solvent ratio is 0.5 ~ 3.5.
5. preparation method according to claim 1, is characterized in that, the DCL/Direct coal liquefaction distillate that described coal direct liquefaction oil is DCL/Direct coal liquefaction full distillate oil or is greater than 180 DEG C for boiling range;
Preferably, described coal direct liquefaction oil is the DCL/Direct coal liquefaction distillate of boiling range 200 ~ 480 DEG C.
6. preparation method according to claim 1, is characterized in that, in described catalytic hydrogenation, catalyst active component is the base metal of VIB and/or VIII; Preferred catalytic agent carrier is amorphous oxide or silicate.
7. preparation method according to claim 6, is characterized in that, the base metal of described group vib is Mo and/or W, and the base metal of described VIII is Co and/or Ni; Preferred described support of the catalyst is amorphous alumina or pure aluminium silicate.
8. preparation method according to claim 7, is characterized in that, in described catalytic hydrogenation, the hydrogenator of employing is fixed-bed reactor, expanded bed reactor or pressure internal recycle ebullated bed reactor;
Alternatively, in described solvent extraction process, the extraction plant of employing is tray column or rotating disc contactor.
9. preparation method according to claim 1, is characterized in that, in described step S3, using described poor aromatic hydrocarbon oil and described light ends oil as Coal Liquefaction Products.
10. a circulation hydrogen supply dissolvent, is characterized in that, adopts the preparation method according to any one of claim 1 to 9 to obtain.
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| US4303498A (en) * | 1979-06-12 | 1981-12-01 | Sumitomo Metal Industries Limited | Process for manufacture of solvent for coal liquefaction |
| US4332666A (en) * | 1980-05-06 | 1982-06-01 | Exxon Research & Engineering Co. | Coal liquefaction process wherein jet fuel, diesel fuel and/or ASTM No. 2 fuel oil is recovered |
| JP2000256678A (en) * | 1999-03-11 | 2000-09-19 | Nippon Mitsubishi Oil Corp | Method for hydro-refining of heavy oil |
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