CN106947559A - A kind of method of coal catalytic hydrogenation gasification production methane and tar light oil - Google Patents
A kind of method of coal catalytic hydrogenation gasification production methane and tar light oil Download PDFInfo
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- CN106947559A CN106947559A CN201710221463.4A CN201710221463A CN106947559A CN 106947559 A CN106947559 A CN 106947559A CN 201710221463 A CN201710221463 A CN 201710221463A CN 106947559 A CN106947559 A CN 106947559A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
-
- 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
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/02—Combustion or pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/04—Gasification
Abstract
A kind of method of coal catalytic hydrogenation gasification production methane and tar light oil is to be supported on the one or two in alkali metal salt, alkali salt, transition metal salt on raw coal as catalyst, the raw coal of supported catalyst is gasified with gasifying agent in fixed bed or fluid bed, gasification temperature is 600 900 DEG C, pressure is 0.1 3MPa, and the flow control of gasifying agent is solid particle at 0.1 10 times of the fluidization number of selected reaction condition；Catalyst in gasification slag is reclaimed by acid extracting, and the filtrate rich in catalyst is concentrated directly to be loaded to afterwards by infusion process in raw coal, is recycling in the catalytic hydrogenation gasification of coal.The present invention has efficiency of carbon con version high, the high advantage of methane content.
Description
Technical field
The invention belongs to coal chemical technology, specifically refer to a kind of for coal catalytic hydrogenation vaporizing system methane and tar light oil
Method.
Background technology
Natural gas from coal technology carries out widely studied having catalytic coal gasifaction technology, coal hydrogenation gasification technology at present, although
All in the technical research stage, but the extensive concern of country and enterprise is received, utilization can because both are carried out directly to coal
Largely by-product tar light oil while methane phase, and efficiency of energy utilization will relative to traditional two-step method preparing natural gas
It is high.
Catalytic coal gasifaction know-why is that fine coal (particle diameter is less than 5mm) and gasifying agent react in the presence of catalyst
Methane is directly generated, using fluidized-bed gasification furnace, about 750 DEG C of reaction temperature, reaction pressure 3.0-4.0MPa exports first in coal gas
Alkane content reaches as high as 25%.Under the support of Department of Science and Technology's supporting plan where Xin Ao energy researches institute and Chinese Academy of Sciences's Shanxi coalification,
Using alkali metal (mainly K in 5t/d process development device2CO3) pressurization that has carried out a variety of coals as catalyst urges
Change gasification test, efficiency of carbon con version will be more than 95%, middle methane of working off one's feeling vent one's spleen more than 2000 hours 2014 device accumulated running times in the end of the year
Content reaches 22%, and methane production is close to 0.5Nm3/ kgC, catalyst recovery yield is more than 98%, solves key technical problem,
But during because vapor more CO, CO can be produced as gasifying agent2Etc. byproduct gas, cause methane selectively still
It is so not high.
Coal hydrogenation gasification be in hydrogen atmosphere, coal dust (particle diameter be less than 0.1mm) be exceedingly fast the rate of heat addition (>104℃/
S), shorter residence time (~10s), H2/ coal (wt/wt%) is 0.2~0.6, certain temperature (~950 DEG C) and pressure
Under the conditions of (~7.0MPa), transient evaporation generation is rich in methane (~50%) and tar light oil (BTX, PCX) in air flow bed
Target product, unconverted semicoke is used for hydrogasification by steam gasification hydrogen manufacturing, is referred to as between gasifying and liquefy it
Between third generation clean coal technology.Its advantage is the content that middle methane of working off one's feeling vent one's spleen greatly improved, but in harsh reaction bar
Efficiency of carbon con version is still relatively low (~50%) under part.
Analyzed based on more than, pressurized fluidized bed gasifier and entrained flow gasification is respectively adopted in catalytic gasification and hydrogasification
Stove, catalytic gasification needs catalyst, and efficiency of carbon con version is higher but outlet methane content is relatively low；Hydrogasification does not need catalyst, goes out
Mouth methane content is higher but efficiency of carbon con version is relatively low.
The content of the invention
The present invention will solve the problem of above-mentioned natural gas from coal technology is present, and propose that a kind of efficiency of carbon con version is high, methane content
High coal catalytic hydrogenation gasification production methane and the method for tar light oil.
The present invention is that the catalytic hydrogenation gasification of coal is applied into fixed bed or fluidized-bed reactor, in shorter solid
Realized in particle residence time more than 90% efficiency of carbon con version, higher methane and the selectivity of tar light oil, and process green
Environmental protection, no NOx、HCN、SOxProduced Deng pollutant.
The technical solution used in the present invention is：
(1) mode of supported catalyst is equi-volume impregnating or dry pigmentation in raw coal；
(2) raw coal of supported catalyst is gasified with gasifying agent in fixed bed or fluid bed, and gasification temperature is 600-
900 DEG C, pressure is 0.1-3MPa, and the flow control of gasifying agent is 0.1- of the solid particle in the fluidization number of selected reaction condition
10 times；
(3) catalyst in gasification slag is reclaimed by acid extracting, the filtrate rich in catalyst, concentrated rear directly logical
Cross infusion process to load in raw coal, be recycling in the catalytic hydrogenation gasification of coal.
Raw coal is to dry base bituminous coal or lignite in the step (1), and particle size range is 20-200 mesh.
Catalyst is the one or two in alkali metal salt, alkali salt, transition metal salt in the step (1).Gold
Category salt is sulfate, nitrate, acetate or carbonate, the element in described metal salt comprising Pt, Cu, Fe, Co, Ni, K,
Na, Ca, Mg, Ba or Al.
Further, the preferred transition metal of element and alkali in the catalyst preferably nitrate or acetate, metal salt
Two kinds of elements of metal composition, or two kinds of elements that transition metal and alkaline-earth metal are constituted.Based on atom mass rate, alkaline-earth metal
Or alkali metal：Transition metal mass ratio is 0.05-2.
The medium volume infusion process of step (1) comprises the following steps：
A, weighed from raw coal and take the dried coal samples of 100g, measurement make coal sample incipient impregnation needed for water volume
B, the 0.5%-10% for accounting for dry base coal sample quality by catalyst metal atom gross mass weigh catalyst, by step
(1) volume of water needed for 100g coal samples, calculates the water needed for whole raw coal, catalyst is added to the water, and is made by stirring
Catalyst dissolution, is obtained impregnating mother liquor, and raw coal will be dried afterwards and is poured slowly into dipping mother liquor, and is stirred with agitator,
Carry out simultaneously it is ultrasonically treated, until catalyst thorough impregnation carries out constant temperature water bath and vacuum to sample successively afterwards in coal sample
Drying process, obtains the raw coal of supported catalyst.
Dip time is ultrasonically treated 30-60 DEG C of temperature in 0.1-20h, dipping process in the dipping process, when ultrasonic
Between be 0.1-2h, ultrasound finishes rear water bath processing temperature for 30-60 DEG C, and the constant temperature water bath time is 5-20h, and dipping is finished.Vacuum
80-120 DEG C of drying temperature, vacuum drying time 2-24h.
Dry pigmentation comprises the following steps in the step (1)：
The 0.5%-10% of dry base coal sample quality is accounted for by catalyst metal atom gross mass, catalyst is mixed with raw coal
Close, and be stirred with agitator, until catalyst is well mixed with raw coal, vacuum drying treatment is carried out afterwards, is loaded
The raw coal of catalyst.
The mixing time is 0.5-2h.Vacuum drying temperature is 80-120 DEG C, vacuum drying time 2-24h.
It is intermittence that the raw coal of supported catalyst described in the step (2), which adds the feeding manner of fixed bed or fluid bed,
Charging or continuous feed.
Further, preferred equi-volume impregnating or dry pigmentation when reactor is fixed bed, reactor are excellent when being fluid bed
Select equi-volume impregnating.
Gasifying agent described in the step (2) is pure hydrogen, or the gaseous mixture that hydrogen is constituted with nitrogen, in gaseous mixture
Hydrogen volume fraction is not less than 50%.
Acid described in the step (3) is watery hydrochloric acid, dust technology or dilute sulfuric acid.
Coal hydrogenation gasification process involved in the present invention is as follows：
The first step：Fast pyrogenation
1.1 devolatilization raw materials → CH4,Cv,C+,C-
1.2 volatile matters are hydrogenated with Cv+H→CH4、HCL、H2O, tar, C2-C3
Second step：Interphase fast reaction
2.1 flash hydrogcnations gasification C++H→CH4
2.2 rapid deactivation C++C+→C-
3rd step：Hydrogasification C at a slow speed-+H→CH4
Cv=volatile matter；C+=activated carbon；C-=inertia carbon；HCL=BTX+PCXN；
The problem of inertia carbon reaction rate in the catalytic hydrogenation gasification of coal mainly the 3rd step of solution is slower, in coal hydrogenation
Transition metal/alkali metal/alkaline-earth metal unitary catalyst is introduced in gasification or by transition metal and alkali metal/alkaline-earth metal
The binary catalyst of composition, because transition-metal catalyst has empty d tracks, with stronger absorption dissociation hydrogen, is provided
The ability of hydroperoxyl radical, can not only suppress 2.2 progress, and catalyst is reduced the nanometer grade gold of generation in gasification
Combination of the metal particles to the carbon-carbon bond in coal can have the effect weakened, so as to promote entirely to be hydrogenated to methane containing carbon species
Process.Alkali and alkaline earth metal ions have the ability of certain fracture C-C keys, can promote turning for the inertia carbon in the 3rd step
Change process.
1.1 pyrolytic process and 1.2 volatile matters of coal can be also hydrogenated with after loading unitary or binary catalyst in coal
Journey plays certain catalytic action, can be produced under the appropriate reaction conditions during the first step more volatile matters and
C+, so that play a part of regulate and control early stage pyrolytic process in product be distributed with promote later stage carbon hydrogasification speed.
Transition metal after reaction in unitary/binary catalyst is in the form of metal simple-substance, alkali metal/alkaline-earth metal
To be present in the form of hydroxide in residue after gasifying, catalyst can be reclaimed by acid wash.
Compared with prior art, the present invention has advantages below：
1) addition of catalyst can reduce the activation energy needed for hydrocarbon gasification reaction, improve efficiency of carbon con version and methane is received
Rate, while the reaction condition of harshness can be alleviated.
2) by loading the stable efficiency of carbon con version that suitable catalyst reaction just can reach 91.3% in 30min, react
Time can match with the solid detention time scope of fixed bed/fluidized-bed reactor, and methane yield (carbon-based standard) can
Up to 78.2wt%, HCL yields (dry ash free basis) are up to 2.16wt%.
3) whole catalytic hydrogenation gasification environmental protection, no NOx、HCN、SOxDeng pollutant generation.
4) catalyst can use simple acid extracting i.e. recyclable in residue after gasifying, and the rate of recovery is up to 98.6%, can
Cycle applications are in the catalytic hydrogenation gasification of coal.
Brief description of the drawings
Fig. 1 is the process chart of the present invention
Embodiment
With reference to embodiment, the present invention will be further described in detail, is easy to more clearly understand the present invention.
Embodiment 1：
The bituminous coal that the 20-200 mesh after 12h is dried under pre- prior to the 100 DEG C vacuum of 100g is weighed, deionization is added into coal
Water, the volume of water is 60ml needed for measurement 100g coal incipient impregnations.Weigh 5.9gCa (NO3)2·4H2O, uses 60ml deionizations
Aqueous dissolution is dipping mother liquor.Load weighted 100g in advance is dried in raw coal 3min and is poured slowly into the leaching in ultrasound environments
In stain mother liquor, while being stirred continuously with mechanical agitator, coal sample is set uniformly to be mixed with mother liquor, constant temperature water bath 50 in ultrasonic procedure
℃.Ultrasound is closed after 2h, stops stirring, and by water-bath in continuation constant temperature 12h at 50 DEG C.Impregnate the material in water-bath after finishing
Taking-up is placed in that 12h is dried under 105 DEG C of vacuum environments, is then ground to 20-200 mesh drying for standby.
In advance by reactor N before reaction230min is purged, reactor temperature control is then reached into design temperature to 850 DEG C
Reactor pressure is risen to 3MPa H afterwards2Atmosphere, and control gas feed and rate of discharge to be by mass flowmenter
12NL/min (2 times of minimum fluidization numbers).100g is loaded with into the raw material of catalyst to be added in feed bin before reaction starts, then
Feed hopper boosts to 3.5MPa.After question response system temperature and pressure stability, the lower end valve of feed bin is opened, material is disposable
It is injected into by 3.5MPa pressure in 3MPa reactor, required process is about 10s, is then shut off feed bin valve.Reacted
The volume for collecting gas is collected and recorded with gas meter to the incoagulable gas produced in journey with airbag.React the volatilization that early stage is produced
Divide and rear system is entered by reactor body with the temperature higher than 400 DEG C, condensation separation is carried out by B-grade condensation system, and
Simultaneously by being separated before addition silica wool in outlet front end is real now into condensation with coal dust.
Reacted whole residues are taken out, 0.4mol/L watery hydrochloric acid 500mL is added, in heating side under 60 DEG C of constant temperature simultaneously
The filtrate for filtering, washing extremely filtering after stirring, 1h while hot does not show acidity.By filtrate in isothermal evaporation at 280 DEG C, it is concentrated into
60ml.The Ca reclaimed in concentrate amount can be measured by Ion Density Measurement Instrument (ICP), the Ca rate of recovery is calculated.
Embodiment 2
Weigh the lignite that the 20-200 mesh after 12h is dried under pre- prior to the 100 DEG C vacuum of 100g.Weigh 24.6gNi (NO3)2·
6H2O and 5.2g KNO3, load weighted 100g in advance is dried and is poured slowly into raw coal 3min in catalyst, while being stirred with machinery
Device stirring 0.5h is mixed, coal sample is uniformly mixed with catalyst.Then material is placed under 105 DEG C of vacuum environments and 12h is dried
It is standby afterwards.
In advance by reactor N before reaction230min is purged, reactor temperature control is then reached into design temperature to 850 DEG C
Reactor pressure is risen to 3MPa H afterwards2Atmosphere, and control gas feed and rate of discharge to be 5NL/ by mass flowmenter
Min (0.8 times of minimum fluidization number).100g is loaded with into the raw material of catalyst to be added in feed bin before reaction starts, then given
Feed bin boosts to 3.5MPa.After question response system temperature and pressure stability, the lower end valve of feed bin is opened, material is disposably led to
The pressure for crossing 3.5MPa is injected into 3MPa reactor, and required process is about 10s, is then shut off feed bin valve.Course of reaction
The volume for collecting gas is collected and recorded with gas meter to the incoagulable gas of middle generation with airbag.React the volatile matter that early stage is produced
Rear system is entered by reactor body with the temperature higher than 400 DEG C, condensation separation is carried out by B-grade condensation system, and together
When by added in outlet front end silica wool it is real now into condensation before separated with coal dust.
Reacted whole residues are taken out, 0.5mol/L dilute sulfuric acid 500mL is added, in heating side under 60 DEG C of constant temperature simultaneously
The filtrate for filtering, washing extremely filtering after stirring, 1h while hot does not show acidity.Filter can be measured by Ion Density Measurement Instrument (ICP)
The Ni and K amount reclaimed in liquid, calculates Ni, K rate of recovery.
Embodiment 3
The bituminous coal that the 20-200 mesh after 12h is dried under pre- prior to the 100 DEG C vacuum of 100g is weighed, deionization is added into coal
Water, the volume of water is 60ml needed for measurement 100g coal incipient impregnations.Weigh 24.6gCo (NO3)2·6H2O and 5.9g Ca
(NO3)2·4H2O, is mixed and turns into dipping mother liquor with the dissolving of 60ml deionized water solutions.Advance load weighted 100g is done
It is poured slowly into dry raw coal 3min in the dipping mother liquor in ultrasound environments, while being stirred continuously with mechanical agitator, makes coal sample
Uniformly mixed with mother liquor, 50 DEG C of constant temperature water bath in ultrasonic procedure.After 2h close ultrasound, stop stirring and by water-bath at 50 DEG C after
Continuous constant temperature 12h.Material in water-bath is taken out and is placed in that 12h, Ran Houyan is dried under 105 DEG C of vacuum environments by dipping after finishing
It is milled to 20-200 mesh drying for standby.
In advance by reactor N before reaction230min is purged, reactor temperature control is then reached into design temperature to 750 DEG C
Reactor pressure is risen into 2MPa, H afterwards2Partial pressure is 1MPa, N2Partial pressure is 1MPa, and controls gas feed by mass flowmenter
5NL/min (3 times of minimum fluidization numbers) is with rate of discharge.100g is loaded with into the raw material of catalyst to add before reaction starts
Into feed bin.After question response system temperature and pressure stability, the auger being connected with feed bin is opened, the pressure for maintaining auger is
2MPa, and material is added continuously in reactor with 20.0g/min speed.The incoagulable gas produced in course of reaction is used
The volume for collecting gas is collected and recorded with gas meter to airbag.The volatile matter of early stage generation is reacted to be not less than 400 DEG C of temperature
Rear system is entered by reactor body, condensation separation is carried out by B-grade condensation system, while by outlet front end
Addition silica wool is real now into being separated before condensation with coal dust.
Reacted whole residues are taken out, 0.5mol/L dilute sulfuric acid 500mL is added, in heating side under 60 DEG C of constant temperature simultaneously
The filtrate for filtering, washing extremely filtering after stirring, 1h while hot does not show acidity.By filtrate in isothermal evaporation at 280 DEG C, it is concentrated into
60ml.The Co reclaimed in concentrate and Ca amount can be measured by Ion Density Measurement Instrument (ICP), Co, Ca rate of recovery is calculated.
Embodiment 4
The bituminous coal that the 20-200 mesh after 12h is dried under pre- prior to the 100 DEG C vacuum of 100g is weighed, deionization is added into coal
Water, the volume of water is 60ml needed for measurement 100g coal incipient impregnations.Weigh 24.6gCo (NO3)2·6H2O and 5.9g Ca
(NO3)2·4H2O, is mixed and turns into dipping mother liquor with the dissolving of 60ml deionized water solutions.Advance load weighted 100g is done
It is poured slowly into dry raw coal 3min in the dipping mother liquor in ultrasound environments, while being stirred continuously with mechanical agitator, makes coal sample
Uniformly mixed with mother liquor, 50 DEG C of constant temperature water bath in ultrasonic procedure.After 2h close ultrasound, stop stirring and by water-bath at 50 DEG C after
Continuous constant temperature 12h.Material in water-bath is taken out and is placed in that 12h, Ran Houyan is dried under 105 DEG C of vacuum environments by dipping after finishing
It is milled to 20-200 mesh drying for standby.
In advance by reactor N before reaction230min is purged, reactor temperature control is then reached into design temperature to 850 DEG C
Reactor pressure is risen to 3MPa H afterwards2Atmosphere, and control gas feed and rate of discharge to be by mass flowmenter
12NL/min (2 times of minimum fluidization numbers).100g is loaded with into the raw material of catalyst to be added in feed bin before reaction starts, then
Feed hopper boosts to 3.5MPa.After question response system temperature and pressure stability, the lower end valve of feed bin is opened, material is disposable
It is injected into by 3.5MPa pressure in 3MPa reactor, required process is about 10s, is then shut off feed bin valve.Reacted
The volume for collecting gas is collected and recorded with gas meter to the incoagulable gas produced in journey with airbag.React the volatilization that early stage is produced
Divide and rear system is entered by reactor body with the temperature higher than 400 DEG C, condensation separation is carried out by B-grade condensation system, and
Simultaneously by being separated before addition silica wool in outlet front end is real now into condensation with coal dust.
Whole residues take out, add 0.5mol/L dust technology 1.0L, side and stirred in being heated under 60 DEG C of constant temperature, after 1h
Filter, washed to the not aobvious acidity of filtrate of filtering while hot.By filtrate in isothermal evaporation at 280 DEG C, 60ml is concentrated into.Pass through ion
Concentration detector (ICP) can measure the Co reclaimed in concentrate and Ca amount, calculate Co, Ca rate of recovery.
Comparative example 1
The bituminous coal that the 20-200 mesh after 12h is dried under pre- prior to the 100 DEG C vacuum of 100g is weighed, it is follow-up without any processing
Processing is in check experiment standby in drier, to gasify as raw coal catalytic hydrogenation.In advance by reactor N before reaction2Blow
Sweep 30min and then by reactor temperature control to 850 DEG C, reach the H that reactor pressure is risen to 3MPa after design temperature2Atmosphere, and
Gas feed and rate of discharge is controlled to be 12NL/min (2 times of minimum fluidization numbers) by mass flowmenter.100g raw materials are existed
Reaction is added in feed bin before starting, and then feed hopper boosts to 3.5MPa.After question response system temperature and pressure stability, open
The lower end valve of feed bin, material is disposably injected into 3MPa reactor by 3.5MPa pressure, required process is about
10s, is then shut off feed bin valve.The incoagulable gas produced in course of reaction is collected with airbag and collects gas with gas meter record
The volume of body.The volatile matter for reacting early stage generation enters rear system with the temperature higher than 400 DEG C by reactor body, passes through two
Level condenser system carries out condensation separation, while by added in outlet front end silica wool it is real now into condensation before and coal dust
Separation.
The ature of coal fundamental analysis data for bituminous coal/lignite that four embodiments and comparative example 1 are used are shown in Table 1.
The gasification result that four embodiments and comparative example 1 of the present invention complete operation 30min after sample introduction is shown in Table 2.
The catalyst of the present invention reclaims and the results are shown in Table 3.
The ature of coal fundamental analysis data of table 1.
2 four embodiments of table and comparative example 1 complete the gasification result after operation 30min after sample introduction.
The catalyst recovery yield result of table 3
To have by table 2, the data without catalyst carry out the raw coal after contrast discovery, supported catalyst and are applied to fluid bed
Higher methane yield and tar yield can be obtained within a short period of time by carrying out catalytic hydrogenation gasification.Comparative example 3 and implementation
Example 4 is it can be seen that the different application conditions of same catalyst have large effect to the transforming degree of coal.Can be with by embodiment 4
See that catalytic hydrogenation gasification may be such that the conversion ratio of bituminous coal reaches that 91.3%, particularly methane and tar light oil are total in 30min
Selectively up to 87.3%, methane volumetric fraction is up to 91.6% in carbonaceous gas, and the yield of methane is without the original under catalysts conditions
Coal embodies catalyst high catalytic activity during the course of the reaction in same 3.4 times of gasification condition.The data of table 3 prove catalyst
It can be reclaimed and be recycled by simple acid extracting.The conversion ratio and methane of high carbon content in coal, tar are selectively broken through
Coal low limitation of severe reaction conditions, reaction time length, conversion ratio during hydrogasification, this is the gasification of coal catalytic hydrogenation
The further amplification of methane and tar light oil processed simultaneously is moved towards to apply there is provided practicable reference frame and thinking, and the present invention is
Efficient, economic, the environmentally friendly natural gas from coal new technique route of one suitable fluidized-bed gasification furnace.
Embodiments described above is to propose the preparation based on raw coal catalytic hydrogenation gasified raw material and application conditions
A part of embodiment, rather than whole embodiments, based on the embodiment in the present invention, this area scientific research and technical staff are not having
The other embodiments obtained on the premise of making creative work, belong to the scope of protection of the invention.
Claims (17)
1. a kind of method of coal catalytic hydrogenation gasification production methane and tar light oil, it is characterised in that comprise the following steps：
(1) mode of supported catalyst is equi-volume impregnating or dry pigmentation in raw coal；
(2) raw coal of supported catalyst is gasified with gasifying agent in fixed bed or fluid bed, and gasification temperature is 600-900
DEG C, pressure is 0.1-3MPa, and the flow control of gasifying agent is 0.1-10 of the solid particle in the fluidization number of selected reaction condition
Times；
(3) catalyst in gasification slag is reclaimed by acid extracting, the filtrate rich in catalyst, and concentrated rear directly pass through is soaked
Stain method is loaded in raw coal, is recycling in the catalytic hydrogenation gasification of coal.
2. the method for a kind of coal catalytic hydrogenation gasification production methane as claimed in claim 1 and tar light oil, it is characterised in that
Raw coal is to dry base bituminous coal or lignite in the step (1), and particle size range is 20-200 mesh.
3. the method for a kind of coal catalytic hydrogenation gasification production methane as claimed in claim 1 and tar light oil, it is characterised in that
Catalyst is the one or two in alkali metal salt, alkali salt, transition metal salt in the step (1).
4. the method for a kind of coal catalytic hydrogenation gasification production methane as claimed in claim 3 and tar light oil, it is characterised in that
Catalyst is two kinds that transition metal and alkali metal are constituted, or two kinds of transition metal and alkaline-earth metal composition, by atomic mass
Than meter, alkaline-earth metal or alkali metal：Transition metal mass ratio is 0.05-2.
5. the method for a kind of coal catalytic hydrogenation gasification production methane as claimed in claim 3 and tar light oil, it is characterised in that
The metal salt is sulfate, nitrate, acetate or carbonate.
6. the method for a kind of coal catalytic hydrogenation gasification production methane as claimed in claim 5 and tar light oil, it is characterised in that
The catalyst is nitrate or acetate.
7. the method for a kind of coal catalytic hydrogenation gasification production methane as claimed in claim 3 and tar light oil, it is characterised in that
Element in the metal salt includes Pt, Cu, Fe, Co, Ni, K, Na, Ca, Mg, Ba or Al.
8. the method for a kind of coal catalytic hydrogenation gasification production methane as claimed in claim 1 and tar light oil, it is characterised in that
The medium volume infusion process of step (1) comprises the following steps：
A, weighed from raw coal and take the dried coal samples of 100g, measurement make coal sample incipient impregnation needed for water volume
B, the 0.5%-10% for accounting for dry base coal sample quality by catalyst metal atom gross mass weigh catalyst, by step（1）
The volume of water needed for 100g coal samples, calculates the water needed for whole raw coal, catalyst is added to the water, and makes catalysis by stirring
Agent is dissolved, and obtains impregnating mother liquor, and raw coal will be dried afterwards and is poured slowly into dipping mother liquor, and is stirred with agitator, simultaneously
Progress is ultrasonically treated, up on catalyst thorough impregnation to coal sample, carrying out constant temperature water bath and vacuum drying to sample successively afterwards
Processing, obtains the raw coal of supported catalyst.
9. the method for a kind of coal catalytic hydrogenation gasification production methane as claimed in claim 7 and tar light oil, it is characterised in that
Dip time is ultrasonically treated 30-60 DEG C of temperature in 0.1-20h, dipping process in the dipping process, and ultrasonic time is 0.1-
2h, it is 30-60 DEG C that ultrasound, which finishes rear water bath processing temperature, and the constant temperature water bath time is 5-20h, and dipping is finished.
10. the method for a kind of coal catalytic hydrogenation gasification production methane as claimed in claim 7 and tar light oil, it is characterised in that
80-120 DEG C of the vacuum drying temperature, vacuum drying time 2-24h.
11. the method for a kind of coal catalytic hydrogenation gasification production methane as claimed in claim 1 and tar light oil, it is characterised in that
Dry pigmentation comprises the following steps in the step (1)：
The 0.5%-10% of dry base coal sample quality is accounted for by catalyst metal atom gross mass, catalyst is mixed with raw coal, and
It is stirred with agitator, until catalyst is well mixed with raw coal, vacuum drying treatment is carried out afterwards, supported catalyst is obtained
Raw coal.
12. the method for a kind of coal catalytic hydrogenation gasification production methane as claimed in claim 10 and tar light oil, its feature exists
Mixing time is 0.5-2h in the dry mixing process.
13. the method for a kind of coal catalytic hydrogenation gasification production methane as claimed in claim 10 and tar light oil, its feature exists
In the vacuum drying temperature be 80-120 DEG C, vacuum drying time 2-24h.
14. the method for a kind of coal catalytic hydrogenation gasification production methane as claimed in claim 1 and tar light oil, it is characterised in that
The raw coal of supported catalyst described in the step (2) adds the feeding manner of fixed bed or fluid bed for intermittent charging or connected
Continuous charging.
15. the method for a kind of coal catalytic hydrogenation gasification production methane as claimed in claim 1 and tar light oil, it is characterised in that
Equi-volume impregnating is used when the reactor is fluid bed.
16. the method for a kind of coal catalytic hydrogenation gasification production methane as claimed in claim 1 and tar light oil, it is characterised in that
Gasifying agent described in the step (2) is pure hydrogen, or the gaseous mixture that hydrogen is constituted with nitrogen, hydrogen volume in gaseous mixture
Fraction is not less than 50%.
17. the method for a kind of coal catalytic hydrogenation gasification production methane as claimed in claim 1 and tar light oil, it is characterised in that
Acid described in the step (3) is watery hydrochloric acid, dust technology or dilute sulfuric acid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109482220A (en) * | 2018-09-19 | 2019-03-19 | 石河子大学 | A kind of composition for carbon catalytic hydrogenation methane |
| CN110713844A (en) * | 2019-10-17 | 2020-01-21 | 中国科学院山西煤炭化学研究所 | Method for co-producing methane and light liquid tar by catalytic hydro-gasification two-step method |
| KR20230052649A (en) * | 2021-10-13 | 2023-04-20 | 울산과학기술원 | Hydrocarbon manufacturing method and hydrocarbons manufactured using the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555420A (en) * | 2008-12-19 | 2009-10-14 | 新奥科技发展有限公司 | Method, system and equipment for catalytic coal gasification |
| CN104174402A (en) * | 2013-05-24 | 2014-12-03 | 中国石油化工股份有限公司 | Catalyst for medium and low temperature catalytic coal gasification for producing natural gas and preparation method thereof |
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2017
- 2017-04-06 CN CN201710221463.4A patent/CN106947559B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101555420A (en) * | 2008-12-19 | 2009-10-14 | 新奥科技发展有限公司 | Method, system and equipment for catalytic coal gasification |
| CN104174402A (en) * | 2013-05-24 | 2014-12-03 | 中国石油化工股份有限公司 | Catalyst for medium and low temperature catalytic coal gasification for producing natural gas and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109482220A (en) * | 2018-09-19 | 2019-03-19 | 石河子大学 | A kind of composition for carbon catalytic hydrogenation methane |
| CN110713844A (en) * | 2019-10-17 | 2020-01-21 | 中国科学院山西煤炭化学研究所 | Method for co-producing methane and light liquid tar by catalytic hydro-gasification two-step method |
| KR20230052649A (en) * | 2021-10-13 | 2023-04-20 | 울산과학기술원 | Hydrocarbon manufacturing method and hydrocarbons manufactured using the same |
| KR102639730B1 (en) * | 2021-10-13 | 2024-02-23 | 울산과학기술원 | Hydrocarbon manufacturing method and hydrocarbons manufactured using the same |
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