CN1243813C - Coal directly-liquifying process with series counter-current and circulating coal-liquifying reactor - Google Patents
Coal directly-liquifying process with series counter-current and circulating coal-liquifying reactor Download PDFInfo
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- CN1243813C CN1243813C CN 03102672 CN03102672A CN1243813C CN 1243813 C CN1243813 C CN 1243813C CN 03102672 CN03102672 CN 03102672 CN 03102672 A CN03102672 A CN 03102672A CN 1243813 C CN1243813 C CN 1243813C
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Abstract
The present invention relates to a direct coal liquefaction process, and the process leads a counter flow reactor, a circulating reactor and a coal liquefied oil (which contains circulation solvent) on-line hydrogenation reactor are connected in series. The present invention belongs to the field of coal chemistry processing. More specifically, the present invention relates to a direct coal hydrogenation liquefaction process, which leads the counter flow reactor, the circulating reactor and the solvent on-line hydrogenation reactor to be connected in series, namely a China direct coal liquefaction process which is called CDCL process for short. The present invention is characterized in that the counter flow reactor and the circulating reactor are connected in series to be used for the coal hydrogenation liquefaction process, and simultaneously, solvent hydrogenation operation and liquified oil stabilized hydrogenation operation are carried out in coal hydrogenation liquefaction operation in a serial mode; in the counter flow reactor which is relatively mild, generated oil directly enters the on-line hydrogenation reactor; coal and heavy liquified oil which are not easily liquified enter the circulating reactor. The yield of oil is high.
Description
Technical field
The invention belongs to the coal chemistry manufacture field of DCL/Direct coal liquefaction, specifically, be a kind of adverse current, circulation, the placed in-line coal direct liquefaction method of online hydrogenator, i.e. CHINESE COAL direct liquefaction technology (China Direct Coal Liquefaction Process abbreviates CDCL technology as).
Background technology
The gelatin liquefaction reactor is one of the most key equipment in the DCL/Direct coal liquefaction technology.The form of gelatin liquefaction reactor and their combination are used in the characteristic that has determined DCL/Direct coal liquefaction technology to a great extent.The reactor of DCL/Direct coal liquefaction process using in the world mostly is the loop reactor of single bubbling bed, fluidized-bed or band pump circulation etc. at present.It is shorter at reactor residence time that these single reaction vessels are difficult to satisfy simultaneously the lightweight liquiefied product of gelatin liquefaction reaction, and difficult liquefaction coal and heavy Coal Liquefaction Products are long and with gas phase hydrogen higher rate of mass transfer and the requirement in long reaction times are arranged at reactor residence time.
Summary of the invention
The object of the present invention is to provide a kind of these requirements that can satisfy above-mentioned prior art existence preferably simultaneously, improve the gelatin liquefaction reaction efficiency, increase adverse current, circulation, the placed in-line coal direct liquefaction method of online hydrogenator of gelatin liquefaction liquid yield.
Adverse current provided by the invention, circulation, the placed in-line coal direct liquefaction method of online hydrogenator are that first section counter-current reactor (or claiming counter-current reactor) and second section internal recycle loop reactor (or claiming internal recycle loop reactor or loop reactor) series connection are used for coal hydrogenation liquefaction process (method) (is same implication in patent application of the present invention) and simultaneously online hydrogenator are combined to a kind of coal Direct Hydrogenation liquefaction method (see figure 1) that coal hydrogenation liquefaction is used for the solvent hydrogenation.Pretreated coal dust is made pumpable coal slurry with the circulating solvent of hydrogenation and the Fe-series catalyst of high dispersive in coal slurry preparation jar V1.Coal slurry is through the high-pressure coal pulp pump P1 and the H that partly circulates
2Enter coal slurry preheater F1 after the mixing together, make coal slurry be heated to 350~450 ℃.Coal slurry after the preheating enters first section counter-current reactor R1 from the top of first section counter-current reactor R1, and coal slurry flows to the bottom from the top of counter-current reactor.Circulation H from the first high-temperature separator V2
2Through (first recycle gas) H
2Behind the compressor C1, a part goes the high-pressure coal slurry pump discharge to mix with coal slurry to prevent coal slurry coking in preheater, most of recycle gas (H wherein
2Concentration is 60% to 80%) enter reactor from first section counter-current reactor bottom and form adverse current with coal slurry from counter-current reactor top.Compare among the demulcent counter-current reactor R1 in temperature of reaction, temperature of reaction is in 400-450 ℃ of scope usually.In the coal than the part that is easier to liquefy at first in hydrogenation liquefaction, the especially coal oxygen-containing functional group at first hydrogenation generate water and phenol products, this partial liquefaction product enters the first high-temperature separator V2 by water cooler L1 together with recycle gas.At first high-temperature separator, through gas-liquid separation, gas circulation is used, H in this gas
2Concentration is about 60% to 80%, and some recycle gas (high pressure exhaust gas) of removing remove H
2Reclaim and purification system.Oil in the liquid further separates with water, and water is sent to treatment unit for waste water and handles.Oil is delivered to the dephenolize unit and is taken off the overhead oil of coming with underpressure distillation unit U1 behind the crude phenols and second high-temperature separator V3 top stream material and enter online hydrogenator R3 and carry out shortening.
H in the gas that first high-temperature separator comes out
2Concentration is about 60% to 80%, and some recycle gas of draining remove H
2Reclaim and purification system, replenish some high H simultaneously from the second high-temperature separator V3
2The recycle gas of concentration, H in the gas that second high-temperature separator comes out
2Concentration about 75% to 95%, be preferably 85% to 90%.So just guaranteed to enter the H in the first circulating air compressor recycle gas
2Concentration maintains certain level.
Described first section counter-current reactor has the function that fluid level control system guarantees that this reactor possesses the coal hydrogenation reactor and also has the function of separator outward, and the separated space that has can account for 10% to 90% of whole reactor.First section counter-current reactor can be bubbling bed reactor, also can be loop reactor.
The coal that relatively is difficult in the counter-current reactor liquefy is discharged from the counter-current reactor bottom with heavy liquiefied product and coal mineral, catalyzer, enters second section internal recycle loop reactor R2 (or claim the internal recycle loop reactor or be called for short loop reactor).The mass flow that enters the internal recycle loop reactor is subjected to the control of liquid level in first section counter-current reactor.Owing to enter internal recycle loop reactor material is difficult part with liquefaction, so internal recycle loop reactor reaction conditions is relatively harsher, temperature is higher than the temperature of first section counter-current reactor, is 400~470 ℃.Fresh H
2Through fresh H
2Compressor C0 with from (second circulation) H
2The circulating hydrogen of compressor C2 enters H after mixing
2Preheater F3.Enter H in the recycle gas of internal recycle loop reactor
2Concentration also is higher than H in the recycle gas that enters counter-current reactor
2Concentration is 75% to 95%.The guide shell of recycle gas bottom the logistics from counter-current reactor enters the internal recycle loop reactor.Because a large amount of gas enters, make that the density of the material here is less in guide shell, under the effect of upstream, the logistics in the guide shell moves upward again.After flowing out guide shell, gas and liquid vapors entrained solids particle continue to move upward, and leave after water cooler L2 cooling from internal recycle loop reactor top and enter the second high-temperature separator V3; Flow out another part logistics of guide shell, mainly be liquid and solid particulate, because self bigger density and form the effect of bigger static pressure difference with fluid in the guide shell, this part logistics moves downward along the annular space district of loop reactor inwall and guide shell outer wall, forms quick circulation movement thus.The less turbulence difference is little everywhere to make loop reactor inside like this, and bubble distribution and solid particulate distributions are even, uniformity of temperature profile.Because the circulation effect makes under the material situation that mean residence time remains unchanged in loop reactor that enters loop reactor, gas, liquid, solid body contact gear ratio is more abundant, has improved heat transfer, mass-transfer efficiency, so the effect of coal hydrogenation liquefaction is relatively good.
Overhead oil of coming with underpressure distillation unit U1 from the oil of taking off behind the crude phenols (liquefaction oil) and second high-temperature separator V3 top stream material enter online hydrogenator R3 and carry out shortening, and online hydrogenator can be that fixed bed hydrogenation reactor also can be the fluidized-bed hydrogenation reactor.The purpose of shortening is to make the circulating solvent cut fraction hydrogenation obtain the good circulating solvent of hydrogen supply performance, Coal Liquefaction Products oil has also carried out shortening in the solvent catalysis hydrogenation, heteroatomic content such as the N in the oil, S, O have also reduced many, and the processed oil that becomes to meet the market sale requirement for the liquefaction oil following process provides basic raw material.
Behind liquefaction oil and the circulating solvent hydrogenation, from the bottom of the online hydrogenator of fixed bed leave online hydrogenator enter warm separator V4, the liquid of separating from V4 removes to prepare coal slurry as circulating solvent.The gas phase of leaving V4 enters low-temperature separator V5 through supercooler L3, and the gas that leaves V5 removes counter-current reactor through purifying a back part, and major part is removed the internal recycle loop reactor.Liquefaction oil behind the hydrogenation removes air distillation unit U2 after low-temperature separator V5 cooling, obtain gasoline fraction, fraction of diesel oil respectively through air distillation.Gasoline fraction goes reformer unit to reform, and obtains qualified gasoline products through allotment again.Fraction of diesel oil goes to the hydrocracking unit, obtains the satisfactory diesel product of cetane value through hydrocracking.
Coal direct liquefaction method provided by the invention has two recycle hydrogen loops, and first circulation loop is the center with first section counter-current reactor, and hydrogen concentration is low to be 60% to 80%; Second circulation loop is the center with second section internal recycle loop reactor and online hydrogenator, and hydrogen concentration is higher to be 75% to 95%, makes the hydrogen concentration of second section internal recycle loop reactor bring up to 85% to 90%.
Oxygen hydrogenation in the gelatin liquefaction process in the coal generates the reaction of water mainly to carry out in first section counter-current reactor, the water that generates through first high-temperature separator after, leave the gelatin liquefaction reactive system very soon, the content that enters water in the material of online hydrogenator R3 like this significantly reduces, the work atmosphere of the online hydrogenation catalyst in the online hydrogenator of gelatin liquefaction obtains essence ground to be improved, thereby makes the steady running for a long time of online hydrogenator.The solvent that obtains has good hydrogen supply performance, and liquefaction oil is by more stable forming.It is shorter at reactor residence time that adverse current provided by the invention, circulation, the placed in-line coal direct liquefaction method of online hydrogenator can better satisfy the lightweight liquiefied product of gelatin liquefaction reaction simultaneously, difficult liquefaction coal and heavy Coal Liquefaction Products have higher rate of mass transfer and the requirement in long reaction times at reactor residence time than length and with gas phase hydrogen, improve the gelatin liquefaction reaction efficiency, increase the gelatin liquefaction liquid yield.
Description of drawings
Fig. 1 is adverse current, circulation, the placed in-line coal direct liquefaction method process flow diagram of online hydrogenator, and it illustrates as follows:
V1: coal slurry preparation jar; P1: high-pressure coal pulp pump; F1: coal slurry preheater; C0, C1, C2: hydrogen gas compressor.F2, F3: hydrogen preheater; R1: first section counter-current reactor; L1: water cooler; V2: first high-temperature separator; R2: second section internal recycle loop reactor; L2: water cooler; V3: second high-temperature separator; Val2: reducing valve; U1: vacuum flashing unit; P2: flash distillation oil pump; R3: online hydrogenator; V4: middle temperature separator; P3: circulating solvent pump.V5: low-temperature separator; U2 air distillation unit.
Embodiment.
Embodiment 1: a kind of young bituminous coal the results are shown in table 1 at the young bituminous coal of liquefaction result and a kind of China of first section counter-current reactor and second section internal recycle loop reactor and the placed in-line coal direct liquefaction method of online hydrogenator in the liquefaction of traditional coal liquefaction craft of two placed in-line reactors of bubbling bed.
Table 1
R1 | R2 | Hydrogen consumption % | Oil yield % | Gas yield % | Aquatic products rate % | |
The inventive method | 440℃ | 460℃ | 7.0 | 60.5 | 18.5 | 8.6 |
The tradition liquefaction process | 450℃ | 460℃ | 8.7 | 54.3 | 22.0 | 8.9 |
Embodiment 2: a kind of Chinese brown coal the results are shown in table 2 in the liquefaction result of first section counter-current reactor, second section internal recycle loop reactor and the placed in-line coal direct liquefaction method of online hydrogenator and a kind of liquefaction of Chinese brown coal tradition liquefaction process.
Table 2
R1 | R2 | Hydrogen consumption % | Oil yield % | Gas yield % | Aquatic products rate % | |
The inventive method | 430℃ | 455℃ | 9.5 | 56.5 | 18.5 | 20.1 |
The tradition liquefaction process | 450℃ | 455℃ | 8.1 | 51.6 | 22.4 | 22.7 |
Claims (5)
1. an adverse current, circulation, the placed in-line coal direct liquefaction method of online hydrogenator comprise:
(1) pretreated coal dust is made pumpable coal slurry with the Fe-series catalyst of hydrogenation circulating solvent and high dispersive, through the high-pressure coal pulp pump (P1) and the H that partly circulates
2Mix post-heating to 350-450 ℃;
(2) coal slurry after the preheating enters the recycle gas after the compressed preheating, wherein H from first section counter-current reactor (R1) top
2Concentration is 60% to 80%, enter from the bottom and to form adverse current with coal slurry and carry out hydrogenation liquefaction, temperature of reaction is 400-450 ℃, the partial liquefaction product carries out gas-liquid separation by entering first high-temperature separator (V2) after water cooler (L1) cooling together with recycle gas, divided gas flow recycles as recycle gas, You Heshui in the liquid sends to further separation, and water is sent to treatment unit for waste water and handles, and oil enters online hydrogenator (R3) after dephenolize;
(3) discharge material by first section counter-current reactor bottom, with fresh H
2After compression with circulation H
2Enter second section internal recycle loop reactor (R2) by the bottom together after the mixing preheating and carry out coal hydrogenation liquefaction, temperature of reaction is 400-470 ℃, H
2Concentration is 75% to 95%, and again through the isolating top of second high-temperature separator (V3) stream material, and remove residue through underpressure distillation and enter online hydrogenator (R3) together by end fraction after cooling for liquefied product;
(4) enter online hydrogenator (R3) with the overhead oil of underpressure distillation unit (U1) and second high-temperature separator (V3) top stream material and carry out shortening from taking off oil behind the phenol, the liquid that warm separator (V4) is separated in the hydrogenation reaction product warp removes to prepare coal slurry as circulating solvent, gas phase enters low-temperature separator (V5) through water cooler (L3) and separates, the gas that leaves low-temperature separator comes along first section counter-current reactor after purifying, major part is removed second section internal recycle loop reactor, liquefaction oil goes to air distillation unit (U2) to obtain gasoline fraction, fraction of diesel oil respectively.
2. according to the adverse current of claim 1, circulation, the placed in-line coal direct liquefaction method of online hydrogenator is characterized in that first section counter-current reactor is bubbling bed reactor or loop reactor.
3. according to claim 1 adverse current, circulation, the method for the placed in-line DCL/Direct coal liquefaction of online hydrogenator is characterized in that it is 10% to 90% of whole reactor that first section counter-current reactor has separated space.
4. according to claim 1 adverse current, circulation, the method for the placed in-line DCL/Direct coal liquefaction of online hydrogenator is characterized in that online hydrogenator is fixed bed hydrogenation reactor or fluidized-bed hydrogenation reactor.
5. according to claim 1 adverse current, circulation, the method for the placed in-line DCL/Direct coal liquefaction of online hydrogenator is characterized in that the concentration of H2 in second section internal recycle loop reactor is 85% to 90%.
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Cited By (5)
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CN100381540C (en) * | 2006-06-27 | 2008-04-16 | 神华集团有限责任公司 | Method of directly liquifying coal |
CN104419436A (en) * | 2013-08-29 | 2015-03-18 | 任相坤 | Direct coal liquefaction process using inferior oil |
CN104419439A (en) * | 2013-08-29 | 2015-03-18 | 任相坤 | Two-stage hydrogenation based direct coal liquefaction process |
CN104419438A (en) * | 2013-08-29 | 2015-03-18 | 任相坤 | Direct liquefaction process of coal mixed with medium and low temperature coal tar |
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CN105181732B (en) * | 2015-10-15 | 2018-08-07 | 神华集团有限责任公司 | The evaluating apparatus and evaluation method of DCL/Direct coal liquefaction performance |
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2003
- 2003-02-14 CN CN 03102672 patent/CN1243813C/en not_active Expired - Lifetime
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CN104419436A (en) * | 2013-08-29 | 2015-03-18 | 任相坤 | Direct coal liquefaction process using inferior oil |
CN104419439A (en) * | 2013-08-29 | 2015-03-18 | 任相坤 | Two-stage hydrogenation based direct coal liquefaction process |
CN104419438A (en) * | 2013-08-29 | 2015-03-18 | 任相坤 | Direct liquefaction process of coal mixed with medium and low temperature coal tar |
CN104419439B (en) * | 2013-08-29 | 2016-08-17 | 任相坤 | A kind of direct coal liquefaction process of two-stage hydrogenation |
CN108641741A (en) * | 2018-05-23 | 2018-10-12 | 华东理工大学 | A kind of liquefied process of coal multistage composite catalytic hydrogenation |
CN108641741B (en) * | 2018-05-23 | 2021-03-26 | 华东理工大学 | Coal multistage composite catalytic hydrogenation liquefaction process method |
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