CN100567463C - A kind of method of hydrotreating of brown coal directly liquefied circulating solvent - Google Patents
A kind of method of hydrotreating of brown coal directly liquefied circulating solvent Download PDFInfo
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- CN100567463C CN100567463C CNB2007800013508A CN200780001350A CN100567463C CN 100567463 C CN100567463 C CN 100567463C CN B2007800013508 A CNB2007800013508 A CN B2007800013508A CN 200780001350 A CN200780001350 A CN 200780001350A CN 100567463 C CN100567463 C CN 100567463C
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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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/086—Characterised by the catalyst used
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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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/006—Combinations of processes provided in groups C10G1/02 - C10G1/08
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Abstract
The present invention relates to a kind of method of hydrotreating of brown coal directly liquefied circulating solvent; adopt the two reactor flow process; first reactor mainly loads the lower protection type catalyzer of hydrogenation activity; second reactor mainly loads the higher Primary Catalysts of hydrogenation activity; form the catalyzer grating of suitable solvent hydrogenation/dehydrogenation balanced reaction; this method of hydrotreating can make all compounds of hydrogenation solvent reach uniformly not exclusively saturation ratio on molecular structure; improve the transferable hydrogen richness in its molecule; thereby make the free hydrogen that circulating solvent discharges (H) just can satisfy the consumption hydrogen needs of brown coal direct liquefaction under the mitigation condition; can simplify the technological process of brown coal liquefaction and solvent hydrogenation; reduce equipment requirements, reduce investment outlay and process cost.
Description
Technical field
The present invention relates to the method for hydrotreating of a kind of method of hydrotreating of coal liquefaction solvent, particularly a kind of brown coal directly liquefied circulating solvent.
Background technology
The coal direct liquefaction method, generally be at high temperature (400～500 ℃) high pressure (under 10.0～30.0MPa) conditions, coal and solvent oil are carried out shortening, generate the high liquid fuel product of hydrogen-carbon ratio, be used for replenishing and replacing the oil fuel product of worsening shortages.In existing various coal direct liquefaction technologies, what have has carried out hydrotreatment to solvent, makes solvent have certain hydrogen supply effect.As the NEDOL process using fixed bed hydrogenation technology of hydrogen supply dissolvent (EDS) technology of Exxon company and Japan specially to the IGOR of circulating solvent hydrogenation, Germany
+Technology and CHINESE COAL direct liquefaction technology (Chinese patent application CN03102672.9) isolate after with the liquefied product hydrogenation circulating solvent, Russian low-pressure liquefied technology and Japanese brown coal liquefaction process (BCL technology and NBCL technology) with hydrogenation and not the hydrogenation solvent be that circulating solvent uses.Although above-mentioned technology makes solvent have the hydrogen supply effect to some extent, the transferable hydrogen in the solvent still can not satisfy the consumption hydrogen needs of higher coal conversion, all needs to add in liquefaction reaction a large amount of gaseous hydrogen.
The fixed bed hydrogenation technology is mainly used in the oil secondary processing, also begins to be used for the upgrading processing of gelatin liquefaction product recently, generally is divided into hydrofining and hydrocracking two class technologies, and the former is a purpose with the deep refining of product, and the latter turns to purpose with heavy oil lightweight.Both final products all are the saturated hydrocarbons materials of stable in properties, and therefore existing fixed bed hydrogenation technology is all strengthened hydrogenation reaction, and unsettled unsaturated hydro carbons content is very low in the product.
The effect of solvent hydrogen supply is EDS technology relatively preferably, uses traditional oil hydrogen addition technology to carry out the solvent hydrogenation: trickle-bed reactor, aluminum oxide support Ni-Mo or Co-Mo catalyzer, 370 ℃ of temperature of reaction, reaction pressure 11MPa.Although can control the hydrogenation degree of depth of solvent by the change condition, but the saturation ratio of hydrogenation solvent is still similar to the petroleum products of hydrogenation, the more shallow product of the hydrogenation degree of depth is the mixture of stable hydrocarbon and unsaturated hydrocarbons substantially, can not provide more free hydrogen (H) to satisfy gelatin liquefaction fully and react required.
Summary of the invention
The method of hydrotreating that the purpose of this invention is to provide a kind of brown coal directly liquefied circulating solvent, this method of hydrotreating can make all compounds of hydrogenation solvent reach uniformly not exclusively saturation ratio on molecular structure, can discharge the free hydrogen of maximum in the gelatin liquefaction reaction.
The technical scheme that realizes above-mentioned purpose is as follows:
A kind of method of hydrotreating of brown coal directly liquefied circulating solvent mainly may further comprise the steps:
(1) raw material solvent after the heating and hydrogen enter first reactor from the bottom of first reactor, the protection type catalyst for pre-hydrogenation of the low hydrogenation activity of filling in this first reactor, bed temperature is 280～350 ℃, when the above stream mode of raw material solvent and hydrogen was passed through first reactor, the hydrogenation that carries out solvent took off the pre-hydrotreating reaction of the height unsaturated materials of easy pyrocondensation in impurity reaction and the solvent;
(2) gas-liquid mixture of finishing pre-hydrotreating reaction is discharged from first reactor head, enter second reactor from second reactor bottom, the Primary Catalysts of the high hydrogenation activity of filling in this second reactor, bed temperature is 310～390 ℃, when the above stream mode of gas-liquid mixture is passed through second reactor, flow stream velocity is lower than gas velocity, carries out the appropriate hydrogenation reaction of unsaturated materials and the appropriate dehydrogenation reaction of saturate;
(3) gas-liquid mixture that finishes of hydrogenation reaction is discharged from second reactor head, enters high pressure hot separator and carries out gas-liquid separation.
Preferably, reaction pressure 6～13MPa in described first reactor and second reactor, hydrogen to oil volume ratio 50～150, air speed 0.3～1.2h
-1
Liquid is external phase in first reactor and second reactor, and gas is the bubbling disperse phase.
It is carrier that protection type catalyst for pre-hydrogenation and Primary Catalysts adopt porous refractory inorganic oxide or crystalline silicate respectively, VIB and or VIII family metallic sulfide be active ingredient; The metallic sulfide content of the pre-hydrogenation of described protection type is 10～20m%, has 120～200m
2The specific surface of/g and the pore volume of 0.60～0.80ml/g; The metallic sulfide content of described Primary Catalysts is 30～40m%, has 170～250m
2The specific surface of/g and the pore volume of 0.35～0.45ml/g.
Preferably, the porous refractory inorganic oxide is an aluminum oxide, and crystalline silicate is a zeolite.
The group vib metal is preferably W, Mo; VIII family metal is preferably Co, Ni.
The volume ratio of protection type catalyst for pre-hydrogenation and Primary Catalysts is 0.4～1.2, is preferably 0.8～1.0.
It is carrier that the present invention adopts porous refractory inorganic oxide such as aluminum oxide or crystalline silicate such as zeolite, and the sulfide of VIB or VIII family metal such as W, Mo, elements such as Co, Ni is active ingredient.The protection type catalyzer that described hydrogenation activity is lower, its metallic sulfide content is 10～20m%, has 120～200m
2The specific surface of/g and the pore volume of 0.60～0.80ml/g; The Primary Catalysts that described hydrogenation activity is higher, its metallic sulfide content is 30～40m%, has 170～250m
2The specific surface of/g and the pore volume of 0.35～0.45ml/g.
From the isolated raw material solvent of liquefied product; contain on a small quantity catalyzer is had the impurity element of poisoning effect and the height unsaturated materials of easy pyrocondensation; so it must be earlier through loading first reactor of protection type catalyzer; remove poisonous impurity at a lower temperature; make the pre-hydrogenation of height unsaturated materials; enter second reactor of filling Primary Catalysts then, under comparatively high temps, carry out the appropriate hydrogenation of most of unsaturated materials and the appropriate dehydrogenation reaction of small portion saturate.This high low activity catalyst collocation is used, and can avoid Primary Catalysts to be poisoned and coking by impurity, makes the efficient performance of activity of such catalysts and effectively prolongs catalyzer work-ing life.
The present invention adopts upflowing (overflow bed) reactor, the liquid of beds is external phase, the gas bubbling rises, the liquid upper reaches is passed through, the liquid storage amount of bed is big, the phenomenon that can avoid the petroleum cuts hydrogenation to use the material short circuits such as channel of downflow system (trickle bed) reactor existence always takes place, help the residence time of balanced solvent at reactor, solvent fully contacts with catalyzer, the temperature distribution of homogenize beds, realize not exclusively saturated hydrogenation/dehydrogenation molecular balance of solvent, the possibility of unsaturated hydrocarbons and stable hydrocarbon coexistence in the reduction product is avoided both to coexist and is formed uneven incomplete saturation ratio.
The present invention adopts a kind of catalyzer grating technology and suitable chemical reaction environment is set, under the demulcent processing condition, realize the incomplete saturated hydrogenation of coal liquefaction solvent, make not exclusively saturate increase in the solvent, improve the transferable hydrogen richness in its molecule, thereby make the free hydrogen that circulating solvent discharges (H) just can satisfy the consumption hydrogen needs of brown coal direct liquefaction under the mitigation condition, not need in liquefaction reaction, to add gaseous hydrogen.
Hydro carbons saturation ratio in the raw material solvent is high more, and its molecular structure is stable more, difficultly more discharges free hydrogen under reaction conditions; And highly undersaturated hydro carbons, its molecule not only can not discharge free hydrogen, can absorb free hydrogen on the contrary and make its chemical structure trend stable.Therefore, in the gelatin liquefaction process, not exclusively the hydrogen supply amount of saturated compound is greater than full saturated compound, and highly unsaturated compounds then almost can not hydrogen supply.
In order to obtain to have the solvent of big hydrogen supply amount, the present invention is according to the hydrogenation of hydro carbons and the principle of dehydrogenation reversible reaction each other, adopt catalyzer grating technology and suitable chemical reaction environment is set, the control reversible reaction is issued to balance at the incomplete saturated hydrogenation state of solvent, both made the unsaturated materials appropriateness hydrogenation in the solvent, made the dehydrogenation of saturate appropriateness again.
Because the complicated component of brown coal, the quality discrepancy of different places of production brown coal is very big, and it is bigger that the one-tenth of its liquefied product and circulating solvent thereof is grouped into rangeability, therefore, and the amplitude of accommodation broad of solvent hydrogenation reaction pressure of the present invention, temperature and air speed.But on average, processing condition of the present invention relax manyly than the petroleum cuts hydroconversion condition.
Reactive hydrogen oil ratio of the present invention is 50～150, the hundreds of of reactive hydrogen oil ratio commonly used have been thousand far below the petroleum cuts hydrogenation, avoided the excessive greatly operating mode of hydrogen, guaranteed the incomplete saturated hydrogenation of solvent/dehydrogenation reaction equilibrated chemical environment, a small amount of stable hydrocarbon that helps taking out of from liquefied product carries out appropriate dehydrogenation reaction.
The present invention realizes the incomplete saturated hydrogenation of coal liquefaction solvent under the demulcent processing condition, improve the hydrogen supply amount of solvent, makes the liquefaction reaction of brown coal only depend on the circulating solvent hydrogen supply just can finish under the mitigation condition, and liquefaction process need not to provide the gaseous hydrogen raw material.Therefore the present invention can simplify the technological process of brown coal liquefaction and solvent hydrogenation, reduces equipment requirements, reduces investment outlay and process cost.
Description of drawings
Below in conjunction with description of drawings technical scheme of the present invention.
Fig. 1 is the schema of the method for brown coal liquefied circulating solvent hydrogenation.
1. new hydrogen L1. water cooler
2. raw material solvent P1. hydrogen gas compressor
3. high pressure divided gas flow P2. raw oil pump
4. washing water R1. first reactor
5. phlegma R2. second reactor
6. recycle hydrogen V1. high-pressure gas-liquid separator
7. hydrogenation solvent V2. low-pressure gas-liquid separator.
F1. process furnace
Embodiment
Referring to Fig. 1, raw material solvent 2 enters process furnace F1 heating through merging with the hydrogen (new hydrogen 1+ recycle hydrogen 6) that mixes after hydrogen gas compressor P1 supercharging after the raw oil pump P2 supercharging.Solvent after the heating and hydrogen enter the first reactor R1 from the bottom.The protection type catalyst for pre-hydrogenation of the low hydrogenation activity of filling in the first reactor R1; bed temperature is lower; when the above stream mode of solvent and hydrogen is passed through the first reactor R1; the hydrogenation that carries out solvent takes off the pre-hydrotreating reaction of the height unsaturated materials of easy pyrocondensation in impurity reaction and the solvent; be that most of S, N, O and metallic impurity in the solvent remove through catalytic hydrogenation reaction; the height unsaturated materials of pyrocondensation reaction such as asphaltene, condensed-nuclei aromatics carry out pre-hydrotreating reaction easily, weaken the condensation reaction proneness of these materials.Present embodiment adopts upflowing (overflow bed) reactor, and logistics enters from reactor bottom, discharges from the top, and liquid is external phase in the reactor, and gas is the bubbling disperse phase.
Finish the gas-liquid mixture of pre-hydrotreating reaction and discharge, enter the second reactor R2 from the bottom from the first reactor R1 top.The Primary Catalysts of the high hydrogenation activity of filling in the second reactor R2, bed temperature higher (concrete data are asked for an interview table 1).Because gas phase has reduced hydrogen concentration through first reactor R1 reaction, formed a chemical environment that is fit to the unsaturated hydrogenation balanced reaction of solvent more at the second reactor R2 bed, when the above stream mode of gas-liquid mixture is passed through the second reactor R2, carry out the appropriate hydrogenation reaction of unsaturated materials and the appropriate dehydrogenation reaction of saturate, be that flow stream velocity is lower than gas velocity, and the approximate plug flow regime of the liquid stream bed that overflows, solvent fully contacts with balanced with catalyzer, under suitable reaction pressure and temperature, shortening between dissolved hydrogen in the solvent and solvent molecule/dehydrogenation reversible reaction reaches balance, unsaturated materials appropriateness hydrogenation in the solvent, and from the appropriate dehydrogenation of the small part saturate of gelatin liquefaction product, the hydrogenation solvent reaches hydrogenation saturation ratio uniformly not exclusively on molecular structure, forms a kind ofly can lack maximum release free hydrogen (product H) under the hydrogen environment at high temperature.The gas-liquid mixture that hydrogenation reaction finishes is discharged from the second reactor R2 top, enters high pressure hot separator V1 and carries out gas-liquid separation.
High-pressure gas-liquid separator V1 discharges hydrogenation solvent 7 in the bottom, and high pressure divided gas flow 3 is discharged at the top.Hydrogenation solvent 7 can directly be sent to brown coal liquefaction reaction system and use without decrease temperature and pressure; High pressure divided gas flow 3 main components are H
2, also have small amount of H
2O, H
2S, NH
3With the gas lighter hydrocarbons.High pressure divided gas flow 3 and washing water 4 converge, and through water cooler L1 cooling condensation, enter cold low separator V2 then.Low to divide gas be recycle hydrogen 6, and recycles after new hydrogen 1 mixes, and phlegma 5 comprises waste water+lighter hydrocarbons, and wherein waste water is H
2S, NH
3The aqueous solution Deng water-soluble gas.Phlegma 5 goes lower procedure further to separate, and reclaims the environmental protection treatment of lighter hydrocarbons and waste water.
Adopt pre-hydrogenation special-purpose catalyzer YZC-01 of circulating solvent protection type (please refer to Chinese patent application CN200610035343.7) and main hydrogenation special-purpose catalyzer ZZC-02 (please refer to Chinese patent application CN200610035342.2) to be seated in two placed in-line 600ml reactors respectively by 1: 1 volume ratio; the brown coal liquefied circulating solvent is carried out hydropyrolysis experiment; test conditions is as shown in table 1; stock oil and product characteristics contrast are as shown in table 2; wherein stock oil 1 is used for embodiment 1～4, and stock oil 2 is used for embodiment 5～6.
The YZC-01 catalyzer can prepare as follows:
(1) peptization solution and wet feed preparation
The nickelous nitrate of the ammonium molybdate of 10.0g and 7.3g is added in the distilled water of 300ml and dissolve, the nitric acid 13ml that adds 75m% again stirs, and makes 335.9g acidified metal salt solution.
Whole acidifying metal salt solutions are poured in the 80g aluminum oxide powder stir, make the uniform metal-containing salt peptization of the color and luster solution 415.9g of water content 74.0m%.
Evenly mediate in the macroporous aluminium oxide with above-mentioned peptization solution adding 260g, make the wet feed 675.9g of water content 45.6m%.
(2) wet feed extrusion
Above-mentioned wet feed is put into banded extruder carry out extrusion, the extrusion diameter is 0.8mm.
(3) extrusion drying and roasting
But above-mentioned wet extrusion is put into the deflated High Temperature Furnaces Heating Apparatus, be warmed up to 125 ℃ with 150 ℃/hr speed, freeze-day with constant temperature 2.0hr is warmed up to 450 ℃ more at the same rate, constant temperature calcining 2.0hr, cooling naturally then.
(4) steeping fluid preparation and catalyst soakage
40.0g ammonium molybdate and 16.3g basic nickel carbonate adding 60ml are contained NH
315m%, H
2O
2In the aqueous solution of 12m%, after stirring is dissolved metal-salt fully, with containing NH
3The pH value of the ammoniacal liquor regulator solution of 45m% and 12m% is 10, makes steeping fluid 80ml.
Adopt the spray pickling process, above-mentioned 80ml steeping fluid all evenly is sprayed onto in the dry extrusion of step (3) gained, make the half-dried extrusion that contains the capacity metal.
(5) contain the half-dried extrusion drying and the roasting of capacity metal
But the above-mentioned half-dried extrusion that contains the capacity metal is put into the deflated High Temperature Furnaces Heating Apparatus, be warmed up to 125 ℃ with 150 ℃/hr speed, freeze-day with constant temperature 2.0hr is warmed up to 450 ℃ more at the same rate, constant temperature calcining 2.0hr, and the work in-process catalyzer is made in cooling naturally then.
(6) sulfuration of work in-process catalyzer: with 480mlCS
2Mix in the diesel oil of adding 12000ml, make sulfuration diesel oil.Under 10MPa pressure, keep hydrogen flowing quantity 5000ml/hr simultaneously, the 400g catalyzer that will be contained in tubular reactor with 15 ℃/hr is raised to 160 ℃, behind the constant temperature 2hr, flow velocity with 150ml/hr makes sulfuration diesel oil pass through beds, simultaneously be warmed up to 230 ℃ with 5 ℃/hr, constant temperature 2.5hr (gas phase H under this temperature
2S concentration reaches more than the 5.5v%).After 230 ℃ of constant temperature finish, be raised to 320 ℃ with 6 ℃/hr, constant temperature 2hr is raised to 370 ℃ with 8 ℃/hr, constant temperature 1.5hr at last.Fast cooling to 150 ℃ then, emptying sulfuration diesel oil, constant temperature also keeps hydrogen purge 2hr, finishes sulfuration.
(7) contaminated product of sulphided state catalyzer protection
When the catalyzer that above-mentioned sulfuration finishes draws off while hot, evenly be sprayed on the catalyzer, naturally cool to room temperature then with the fraction oil 80g of 250～400 ℃ of wax content 12m%, the boiling ranges of 80 ℃ of temperature.
The ZZC-02 catalyzer prepares as follows:
(1) peptization solution and wet feed preparation
The nitric acid (concentration 75m%) of 18ml is added in the distilled water of 270ml and dissolve, stir, make the 289.3g salpeter solution.
Whole salpeter solutions are poured in the 80g aluminum oxide powder stir, make the uniform peptization solution of the color and luster 369.3g of water content 74.4%.
Macroporous aluminium oxide (pore volume is 0.62ml/g), 33.3g ammonium molybdate, 28.8 nickelous nitrates of above-mentioned peptization solution and 192g are evenly mediated, made the wet feed 623.4g of water content 43.8m%.
(2) wet feed extrusion
Above-mentioned wet feed is put into banded extruder carry out extrusion, the extrusion diameter is 0.8mm.
(3) extrusion drying and roasting
But above-mentioned wet extrusion is put into the deflated High Temperature Furnaces Heating Apparatus, be warmed up to 125 ℃ with 150 ℃/hr speed, freeze-day with constant temperature 2.0hr is warmed up to 450 ℃ more at the same rate, constant temperature calcining 2.0hr, cooling naturally then.
(4) steeping fluid preparation and catalyst soakage
62.1g ammonium molybdate and 30.0g basic nickel carbonate adding 100ml are contained NH
315m%, H
2O
2In the aqueous solution of 12m%, after stirring is dissolved metal-salt fully, with containing NH
3The pH value of the ammoniacal liquor regulator solution of 45m% and 12m% is 10, makes steeping fluid 130ml.
Adopt the spray pickling process, above-mentioned 130ml steeping fluid all evenly is sprayed onto in the dry extrusion of step (3) gained, make the wet extrusion that contains the capacity metal.
(5) contain the wet extrusion drying and the roasting of capacity metal
But the above-mentioned half-dried extrusion that contains the capacity metal is put into the deflated High Temperature Furnaces Heating Apparatus, be warmed up to 125 ℃ with 150 ℃/hr speed, freeze-day with constant temperature 2.0hr is warmed up to 450 ℃ more at the same rate, constant temperature calcining 2.0hr, and the work in-process catalyzer is made in cooling naturally then.
(6) sulfuration of work in-process catalyzer: with 480mlCS
2Mix in the diesel oil of adding 12000ml, make sulfuration diesel oil.Under 10MPa pressure, keep hydrogen flowing quantity 5000ml/hr simultaneously, the 400g catalyzer that will be contained in tubular reactor with 15 ℃/hr is raised to 160 ℃, behind the constant temperature 2hr, flow velocity with 150ml/hr makes sulfuration diesel oil pass through beds, simultaneously be warmed up to 230 ℃ with 5 ℃/hr, constant temperature 2.5hr (gas phase H under this temperature
2S concentration reaches more than the 5.5v%).After 230 ℃ of constant temperature finish, be raised to 320 ℃ with 6 ℃/hr, constant temperature 2hr is raised to 370 ℃ with 8 ℃/hr, constant temperature 1.5hr at last.Fast cooling to 150 ℃ then, emptying sulfuration diesel oil, constant temperature also keeps hydrogen purge 2hr, finishes sulfuration.
(7) contaminated product of sulphided state catalyzer protection
When the catalyzer that above-mentioned sulfuration finishes draws off while hot, evenly be sprayed on the catalyzer, naturally cool to room temperature then with the fraction oil 70g of 250～400 ℃ of wax content 12m%, the boiling ranges of 80 ℃ of temperature.
Table 1 brown coal liquefied circulating solvent hydropyrolysis experiment condition
| |
1 | 2 | 3 | 4 | 5 | 6 |
| Pressure, MPa | 9.6 | 7.1 | 10.8 | 8.2 | 6 | 13 |
| First temperature of reactor, ℃ | 292 | 301 | 311 | 321 | 348 | 279 |
| Second temperature of reactor, ℃ | 323 | 341 | 350 | 360 | 390 | 310 |
| Air speed, h -1 | 0.3 | 0.2 | 0.25 | 0.25 | 0.65 | 1.2 |
| Hydrogen-oil ratio, v/v | 65 | 85 | 95 | 130 | 150 | 50 |
The data of table 1 show that among the embodiment 1～4, pressure is up to the 10.8MPa of embodiment 3, and minimum is the 7.1MPa of embodiment 2; (temperature is up to 321 ℃ of embodiment 4 to first reactor, and minimum is 292 ℃ of embodiment 1, and second temperature of reactor is up to 360 ℃ of embodiment 4, and minimum is 323 ℃ of embodiment 1; Hydrogen-oil ratio is up to 130 (v/v) of embodiment 4, and minimum is 65 (v/v) of embodiment 1; Air speed is selected 0.2 lower～0.3h
-1, be because the toluene insolubles (24.9m%) and bituminous matter (17.6m%) content in the toluene solvend of stock oil 1 are higher, need the longer reaction times that its hydrocracking is low molecular product.The stock oil 2 of embodiment 5～6, bituminous matter (1.2m%) content in its undesirable components toluene insolubles (4.3m%) and the toluene solvend is lower, and (embodiment 5,6 is respectively 0.65h to adopt higher space velocity
-1And 1.2h
-1) under, carry out the complementary contrast of marginal condition of the present invention of temperature, pressure and hydrogen-oil ratio.Above-mentioned reaction conditions belongs to the medium-pressure hydrocracking category, and temperature of reaction and hydrogen-oil ratio are all lower.
Unsaturated aromatic hydrocarbon in the table 2 and hydrogenated aromatic hydrocarbon materials are by the mass spectrometry quantitative analysis, and wherein the hydrogenated aromatic hydrocarbon materials has comprised the incomplete stable hydrocarbon of various different hydrogenation atom numbers, and saturated small content of cyclic hydrocarbon is integrated in the stable hydrocarbon of group composition fully.
By table 2 as seen, in embodiment 1～4, solvent density (20 ℃) is reduced between 1.10～1.04g/ml of product by the 1.14g/ml of stock oil, and boiling range all has reduction in various degree, illustrates that reaction process of the present invention has reduced the molecular weight of solvent effectively.
The toluene solvend is increased to 85.9～89.3m% of product, amplification 10.8～14.2m% by the 75.1m% of stock oil; Correspondingly toluene insolubles is reduced to 14.1～10.7m% of product by the 24.9m% of stock oil.This shows solvent hydrogenation process of the present invention, and non-aromatics material that can molecular weight is bigger is converted into the material with aromatic ring structure.
Stable hydrocarbon in the toluene solvend is reduced to 0.43～0.73m% of product by the 2.81m% of stock oil, colloid and bituminous matter are reduced to 4.66～6.67m% of product by the 23.45m% of stock oil, and correspondingly aromatic hydrocarbon is increased to 92.81～94.61m% of product by the 73.74m% of stock oil.As seen reaction process of the present invention not only is converted into aromatoising substance with the dehydrogenation of naphthenic hydrocarbon appropriateness, and very effectively that molecular weight is huge condensed ring colloid and the bituminous matter less few aromatic hydrocarbon ring of molecular weight of progressively degrading, and latter's ideal solvent composition just.
Analytical data of mass spectrum shows, unsaturated aromatic hydrocarbon is reduced to 11.05～12.01m% of product significantly by the 53.35m% of stock oil, not exclusively saturated hydrogenated aromatic hydrocarbon is then increased considerably 69.52～72.47m% of product by the 1.46m% of stock oil, this just fairly obvious molecular composition changes, and has improved the hydrogen supply capacity of solvent greatly.
Table 2 stock oil and product characteristics contrast
| |
1 | 2 | 3 | 4 | 5 | 6 | |
|
| Density (20 ℃), kg/m 3 | 1.10 | 1.07 | 1.06 | 1.04 | 1.02 | 1.08 | 1.14 | 1.11 |
| Boiling range, ℃ | ||||||||
| HK | 180 | 156 | 136 | 102 | 102 | 203 | 204 | 223 |
| 50％ | 333 | 323 | 330 | 308 | 303 | 336 | 341 | 365 |
| 90％ | 399 | 390 | 389 | 379 | 371 | 391 | 412 | 398 |
| The toluene solvend, m% | 87.8 | 85.9 | 89.3 | 88.6 | 98.3 | 97.8 | 75.1 | 95.7 |
| Toluene insolubles, m% | 12.2 | 14.1 | 10.7 | 11.4 | 1.7 | 2.2 | 24.9 | 4.3 |
| Group composition (toluene solvend) | ||||||||
| Stable hydrocarbon, m% | 0.52 | 0.71 | 0.73 | 0.43 | 0.62 | 0.88 | 2.81 | 3.02 |
| Aromatic hydrocarbon, m% | 92.81 | 93.78 | 94.61 | 94.45 | 98.6 6 | 98.6 9 | 73.74 | 95.38 |
| Colloid+bituminous matter, m% | 6.67 | 5.51 | 4.66 | 5.12 | 0.72 | 0.43 | 23.45 | 1.60 |
| Unsaturated aromatic hydrocarbon, m% | 11.52 | 11.05 | 12.01 | 11.91 | 22. 31 | 16.2 5 | 53.35 | 75.22 |
| Naphthalene | 1.22 | 1.18 | 1.25 | 1.24 | 2.48 | 1.83 | 7.31 | 9.21 |
| Methylnaphthalene | 0.54 | 0.55 | 0.56 | 0.56 | 1.26 | 0.90 | 2.58 | 3.46 |
| Fluorenes | 0.32 | 0.31 | 0.33 | 0.33 | 0.71 | 0.51 | 3.96 | 5.02 |
| Luxuriant and rich with fragrance | 0.11 | 0.11 | 0.09 | 0.09 | 0.20 | 0.16 | 2.47 | 3.33 |
| Anthracene | 5.81 | 5.61 | 6.23 | 6.17 | 12.33 | 9.01 | 30.12 | 45.34 |
| Pyrene | 3.52 | 3.29 | 3.55 | 3.52 | 5.33 | 3.84 | 6.91 | 8.86 |
| The hydrogenated aromatic hydrocarbon, m% | 69.97 | 69.52 | 72.47 | 71.82 | 80. 13 | 83. 22 | 1.46 | 2.16 |
| Hydrogenated naphthalene | 11.88 | 11.75 | 12.33 | 12.21 | 13.60 | 14.02 | 0 | 0.09 |
| The hydrogenation methylnaphthalene | 5.22 | 4.96 | 5.21 | 5.17 | 5.81 | 5.99 | 0.21 | 0.28 |
| The hydrogenation fluorenes | 6.06 | 6.02 | 6.28 | 6.22 | 6.94 | 7.22 | 0 | 0.06 |
| The hydrogenation phenanthrene | 3.88 | 3.86 | 4.02 | 3.98 | 4.44 | 4.64 | 0.02 | 0.18 |
| The hydrogenation anthracene | 34.68 | 34.80 | 36.21 | 35.92 | 39.99 | 41.67 | 1.23 | 1.49 |
| Hydropyrene | 8.25 | 8.13 | 8.42 | 8.32 | 9.35 | 9.68 | 0 | 0.06 |
In embodiment 5 and embodiment 6, the former pressure and air speed are low than the latter, but temperature and hydrogen-oil ratio are than latter's height.This reaction conditions of two groups has to a certain degree complementarity to reaction result, therefore the character of product is more or less the same, only embodiment 5 is because temperature of reaction is higher and the reaction times is longer, help scission reaction, so its solvent density (20 ℃) is reduced to the 1.02g/ml of product by the 1.11g/ml of stock oil, a little less than the 1.08g/ml among the embodiment 6.The boiling range of embodiment 5 products is lower than the boiling range of embodiment 6, and reason as above.
Pressure among the embodiment 6 is the highest, helps hydrogenation reaction.Too high for the hydrogenation saturation ratio that prevents product, adopted minimum hydrogen-oil ratio and maximum air speed, so the hydrogenated aromatic hydrocarbon content (83.22m%) of this embodiment is only a little more than embodiment 5 (80.13m%) 3.09m%.
The data of table 2 show that because the undesirable components content of stock oil 2 is lower, although its reaction velocity is higher, the hydrogenated aromatic hydrocarbon content of its product still is higher than the hydrogenation products of stock oil 1.
Table 3 hydrogenation solvent and the not brown coal thermally dissolving and catalytic test contrast of hydrogenation solvent
| |
7 | 8 |
| Type of solvent | Hydrogenation | Hydrogenation not |
| Reaction pressure, MPa | 5.2 | 5.2 |
| Temperature of reaction, ℃ | 400 | 400 |
| Reaction times, min | 30 | 30 |
| Agent coal ratio, m/ |
3∶1 | 3∶1 |
| Catalyzer, g | 1.0 | 1.0 |
| Drop into brown coal (daf), g | 250 | 250 |
| Drop into solvent (daf), g | 750 | 750 |
| Discharge coal dust (daf), g | 66.4 | 283.2 |
| Discharge oil (daf), g | 828.1 | 633.0 |
| Drainage water (daf), g | 28.6 | 28.9 |
| Transformation efficiency (daf), m% | 73.44 | -13.28 |
| Oil yield rate (daf), m% | 31.24 | -46.80 |
| Producing water ratio (daf), m% | 11.44 | 11.56 |
| Factor of created gase (daf), the ml/g coal | 111.11 | 112.32 |
The data of table 3 show, under identical agent coal ratio and reaction conditions, the hydrogenation solvent does not have the hydrogen supply effect substantially, unsaturated materials generation condensation that solvent produces with pulverized coal pyrolysis under high temperature and pressure effect and coking reaction, cause liquid to reduce and the solid increase, except that the thermally dissolving and catalytic reaction of producing water ratio and factor of created gase and the participation of hydrogenation solvent was close, transformation efficiency and oil yield rate were negative value.And the hydrogenation solvent has enough hydrogen supply effects, and the hydrogen of its release in time combines the stable liquefied product of generation with the unsaturated materials that pulverized coal pyrolysis produces, and reaches ideal brown coal thermally dissolving and catalytic transformation efficiency and oil yield rate.
Claims (7)
1. the method for hydrotreating of a brown coal directly liquefied circulating solvent, it is characterized in that, mainly may further comprise the steps: solvent after (1) heating and hydrogen enter first reactor from the bottom of first reactor, the protection type catalyzer of the low hydrogenation activity of filling in this first reactor, bed temperature is 280～350 ℃, when the above stream mode of solvent and hydrogen was passed through first reactor, the hydrogenation that carries out solvent took off the pre-hydrotreating reaction of the height unsaturated materials of easy pyrocondensation in impurity reaction and the solvent;
(2) gas-liquid mixture of finishing pre-hydrotreating reaction is discharged from first reactor head, enter second reactor from second reactor bottom, the Primary Catalysts of the high hydrogenation activity of filling in this second reactor, bed temperature is 310～390 ℃, when the above stream mode of gas-liquid mixture is passed through second reactor, flow stream velocity is lower than gas velocity, carries out the appropriate hydrogenation reaction of unsaturated materials and the appropriate dehydrogenation reaction of saturate;
(3) gas-liquid mixture that finishes of hydrogenation reaction is discharged from second reactor head, enters high pressure hot separator and carries out gas-liquid separation;
It is carrier that described protection type catalyzer and described Primary Catalysts adopt porous refractory inorganic oxide or crystalline silicate respectively, and VIB and/or VIII family metallic sulfide are active ingredient; The metallic sulfide content of described protection type catalyzer is 10～20m%, has 120～200m
2The specific surface of/g and the pore volume of 0.60～0.80ml/g; The metallic sulfide content of described Primary Catalysts is 30～40m%, has 170～250m
2The specific surface of/g and the pore volume of 0.35～0.45ml/g.
2, method according to claim 1 is characterized in that, reaction pressure 6～13MPa in described first reactor and second reactor, hydrogen to oil volume ratio 50～150, air speed 0.3～1.2h
-1
3, method according to claim 1 is characterized in that, liquid is external phase in described first reactor and second reactor, and gas is the bubbling disperse phase.
4. method according to claim 1 is characterized in that, described porous refractory inorganic oxide is an aluminum oxide, and described crystalline silicate is a zeolite.
5, method according to claim 1 is characterized in that, described group vib metal is W, Mo; Described VIII family metal is Co, Ni.
6, method according to claim 1 is characterized in that, the volume ratio of described protection type catalyzer and described Primary Catalysts is 0.4～1.2.
7, method according to claim 6 is characterized in that, the volume ratio of described protection type catalyzer and described Primary Catalysts is 0.8～1.
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| CNA2006100353348A CN1844318A (en) | 2006-05-08 | 2006-05-08 | Hydrogenation process for coal direct liquefaction circulation solvent |
| CN200610035334.8 | 2006-05-08 | ||
| PCT/CN2007/001508 WO2007131437A1 (en) | 2006-05-08 | 2007-05-08 | Hydrogenation process for coal direct liquefaction circulation solvent |
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| CN1844318A (en) * | 2006-05-08 | 2006-10-11 | 珠海市三金煤制油技术有限公司 | Hydrogenation process for coal direct liquefaction circulation solvent |
| CN100547055C (en) * | 2007-12-13 | 2009-10-07 | 肇庆市顺鑫煤化工科技有限公司 | A kind of thermally dissolving and catalytic method of producing liquid fuel with brown coal |
| CN101591564B (en) * | 2008-05-29 | 2014-04-09 | 北京三聚环保新材料股份有限公司 | Hydrofining method of diesel oil distillates in direct coal liquefied oil |
| CN102191075A (en) * | 2010-03-17 | 2011-09-21 | 肇庆市顺鑫煤化工科技有限公司 | Lignite solubilizing and catalytic liquefaction method in non-hydrogen atmosphere |
| CN103468314B (en) * | 2013-09-27 | 2016-01-20 | 神华集团有限责任公司 | DCL/Direct coal liquefaction circulating solvent and its preparation method and application |
| CN104194830B (en) * | 2014-08-29 | 2017-01-11 | 神华集团有限责任公司 | Direct coal liquefaction circulating solvent and processing method thereof as well as direct coal liquefaction method utilizing direct coal liquefaction circulating solvent |
| CN106479564A (en) * | 2016-09-21 | 2017-03-08 | 神华集团有限责任公司 | Circulating solvent and preparation method thereof |
| CN108130116A (en) * | 2016-12-01 | 2018-06-08 | 何巨堂 | Preposition solvent oil hydrogenation reaction process and coal hydrogenation liquefaction reaction process combined method |
| CN110003943B (en) * | 2019-05-08 | 2021-04-27 | 胜帮科技股份有限公司 | Device and method for producing hydrogen donor solvent |
| CN113289507B (en) * | 2021-05-10 | 2023-02-03 | 内蒙古旭阳新材料有限公司 | Wet aluminum powder production equipment and method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4303498A (en) * | 1979-06-12 | 1981-12-01 | Sumitomo Metal Industries Limited | Process for manufacture of solvent for coal liquefaction |
| JP2000256678A (en) * | 1999-03-11 | 2000-09-19 | Nippon Mitsubishi Oil Corp | Method for hydro-refining of heavy oil |
| CN1349554A (en) * | 1999-04-13 | 2002-05-15 | 切夫里昂美国公司 | Upflow reactor system with layered catalyst bed for hydrotreating heavy feedstocks |
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| JPS57174389A (en) * | 1981-04-21 | 1982-10-27 | Sumitomo Metal Ind Ltd | Hydrogenation of solvent for coal liquefaction |
| JPH02107333A (en) * | 1988-10-17 | 1990-04-19 | Sumitomo Metal Mining Co Ltd | Catalyst for hydrogenation of circulating solvent for coal liquefaction |
| CN1844318A (en) * | 2006-05-08 | 2006-10-11 | 珠海市三金煤制油技术有限公司 | Hydrogenation process for coal direct liquefaction circulation solvent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4303498A (en) * | 1979-06-12 | 1981-12-01 | Sumitomo Metal Industries Limited | Process for manufacture of solvent for coal liquefaction |
| JP2000256678A (en) * | 1999-03-11 | 2000-09-19 | Nippon Mitsubishi Oil Corp | Method for hydro-refining of heavy oil |
| CN1349554A (en) * | 1999-04-13 | 2002-05-15 | 切夫里昂美国公司 | Upflow reactor system with layered catalyst bed for hydrotreating heavy feedstocks |
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