CN106675610A - Device and method for performing in-situ catalytic modification on volatile components obtained during rapid pyrolysis and coupling pyrolysis of coal - Google Patents
Device and method for performing in-situ catalytic modification on volatile components obtained during rapid pyrolysis and coupling pyrolysis of coal Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 127
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000004048 modification Effects 0.000 title claims abstract description 16
- 238000012986 modification Methods 0.000 title claims abstract description 16
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- 238000010168 coupling process Methods 0.000 title claims abstract description 8
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 title abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 238000001816 cooling Methods 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 230000007246 mechanism Effects 0.000 claims abstract description 14
- 238000007233 catalytic pyrolysis Methods 0.000 claims abstract description 7
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Classifications
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a device and a method for performing in-situ catalytic modification on volatile components obtained during rapid pyrolysis and coupling pyrolysis of coal. The device comprises a catalytic pyrolysis furnace, wherein the catalytic pyrolysis furnace comprises a catalytic fixed furnace and a catalytic movable furnace; the catalytic movable furnace and the catalytic fixed furnace are coaxially arranged up and down; a lifting mechanism is connected to the outer wall of the catalytic movable furnace; a reducing reactor is arranged inside the catalytic fixed furnace; the reducing reactor comprises a pyrolyzing chamber and a catalyzing chamber; the pyrolyzing chamber stretches into the inner cavity of the catalytic movable furnace; the catalyzing chamber is arranged inside the inner cavity of the catalytic fixed furnace. The catalytic fixed furnace and the catalytic movable furnace are independently arranged, and the movable furnace can move up and down, so that rapid heating pyrolysis of a coal sample and rapid cooling of the coal sample after the completion of the pyrolysis are achieved; the catalytic fixed furnace and the catalytic movable furnace are independently arranged in a two-stage manner, and the reducing reactor is adopted, so that by adjusting the layouts of a pyrolyzing section and a catalyzing section and the raw material ratio, an effective catalytic effect can be achieved under the condition that a small amount of catalyst exists, and thus the catalytic cost is reduced; therefore, the device and the method are suitable for industrial popularization and application.
Description
Technical field
The invention belongs to pyrolysis of coal technical field, more particularly to a kind of new multistage porous molecular sieve realizes the fast speed heat of coal
The device and method of decoupling volatiles situ catalytic modification.
Background technology
The low order coal reserves of China is big, and reactivity is good, and oil productivity is high, the middle low temperature coal tar obtained by middle low temperature pyrogenation
Oil, serves not only as vehicle fuel, but also is the important sources for obtaining some industrial chemicals.But directly pyrolysis is obtained low-order coal
In the middle coalite tar for taking, heavy ingredient content is high, this not only lowers the quality of tar, and its full-bodied characteristic
Some arrange difficult to cause industrial separation, operation etc..Therefore, the raising of tar yield and quality is realized, to pyrolysis of coal industry
And the development of country has far-reaching influence.
It is well known that pyrolytic process condition has a very big impact to pyrolysis of coal conversion ratio and products distribution.Wherein heat up
The raising of speed effectively accelerates the precipitation of volatiles, makes primary decomposition product time of contact short with coal grain, reduces and waves
The chance that stimulating food secondary response occurs, and have very strong impulsive force to coal molecule due to being rapidly heated, promote chemical bond simultaneously
Fracture generates more small molecule segment, so as to promote the raising of corresponding tar light components.Therefore, realize that coal fast pyrogenation draws
Play people to pay attention to, realize that coal fast pyrolysis process mainly has microwave-assisted coal fast pyrogenation and traditional heating stove to realize that coal is fast at present
Speed heat solution.Microwave-heating effectively realizes being rapidly heated for coal sample, overcomes the uneven deficiency of heat transfer, but its is expensive,
Complex process, in long-time industrial development cannot be met.Traditional heating stove realizes that fast pyrogenation mainly has two ways, Yi Zhongshi
Reaction tube is heated up by heating furnace, when temperature rises to desired temperature, coal sample is poured into into reaction from reactor top
Pipe in, due to this kind of method adulterate during coal sample is toppled over air entrance, a part of coal sample can be burnt, the meter to the later stage
Calculation causes difficulty, and whole process operation difficulty degree is big, difficult with this realization of industrialization.Another kind is that early stage fills coal sample
In being loaded in corbeil, the top of reactor is placed in, when stove to be heated rises to desired temperature, corbeil is put down, realize fast pyrogenation.But
Because this kind of method is to fall to reactor by top, therefore part-time length is twitched up and down also due to abrasion causes airtight
Property be deteriorated, the problems such as air is entered.Therefore have to usually change accessory, and for a large amount of coal samples, manual operation coefficient is big, just
For economic and practical, this kind of method is also unfavorable for industrialized development.
Hydropyrolysis and catalysis pyrolysis are capable of achieving the raising of the coal-tar middle oil quality of pyrolytic process.But, hydropyrolysis need
Substantial amounts of hydrogen is expended, and hydrogen making expends substantial amounts of energy, adds a series of equipment such as hydrogen manufacturing and gas separation, increases
Industry cost, then people sight is focused in catalysis pyrolysis.The introducing of catalyst not only improves pyrolysis of coal conversion ratio, real
Show thermal decomposition product distribution and oriented conversion, and effectively relax pyrolytical condition.In order to realize tar upgrading, to improve heat
Catalyst in solution tar for the purpose of light oil content should select iron-based, Ni-based, molecular sieve catalyst containing Mo, Co.Wherein molecule
Sieve catalyst has carrier and catalyst dual-use function concurrently, and activity is high and with selectivity of product, mainly adopts in current research
Traditional single micro porous molecular sieve is used as low order coal pyrolysis catalyst.Active metal Mo and Ni are supported on HZSM-5 point by Yan Lunjing
Son is sieved for the modification of pyrolysis of coal tar situ catalytic, is as a result found, Jing HZSM-5 catalysis brown coal (XM) pyrolysis light aromatics total amounts
Increment rate be 220%, after supported active metals Mo and Ni, the generation of light aromatics can be effectively facilitated, Ni is to band in tar
Aliphatic side chainses compound has higher splitting action, and Mo is then conducive to how band practices the shape of compound such as toluene and dimethylbenzene
Into.In two-part fixed bed, nickel-base catalyst is supported on ZSM-5 to be carried out Muhammad Nadeem Amin to low-order coal
Catalysis pyrolysis, research finds that the ZSM-5 catalyst for loading NiO not only increases the yield of tar light oil (such as carbolic oil, naphtalene oil),
And effectively reduce the content of the N in tar and S.Therefore, during catalysis pyrolysis low-order coal, molecular sieve is for excellent
Change, obtain chemical products with high added-value and have great importance.Kong Xiaojun is adopted with super-stable Y molecular sieves (USY) as catalyst
Py-GC/MS has investigated impact of the USY molecular sieve to pyrolysis of coal, as a result shows：USY molecular sieve can effectively facilitate the weight such as PAHs
Matter component to light components cracking is converted.Jing after USY molecular sieve catalysis, the BTEXN yields obtained by He Xi coals are increased by 1.5wt%
To 4.5wt%, while 3~4 ring polycyclic aromatic hydrocarbon gross production rates reduce respectively 32.8%.Chen Jingsheng utilizes TG-FTIR technical research
Impact of the CoMoP/13X catalyst to loess mausoleum pyrolysis of coal weight-loss and gaseous product Conduce Disciplinarian, research shows：In hydrogen
Atmosphere encloses light aromatics compound growing amount maximum in the presence of lower CoMoP/13X catalyst, and it is probably CoMoP/13X catalyst
On CoMo activity promote hydrogen relay into hydroperoxyl radical so that the free radical containing phenyl ring that pyrolytic process is generated is by stable in time
Get off, so as to generate more light aromatics materials, this is likely to relevant with the physicochemical characteristic such as the duct of 13X and acidity.
Gang Yao by the H-beta molecular sieves for being loaded with ruthenium element have dual-use function catalyst be used for lignin hydrogenation deoxidation with
Phenolic monomers and dimer are removed, the purpose for improving bio oil upgrading is reached.Research shows, is 413k in temperature, and pressure is
Under 4Mpa mild operating conditionses, Ru/H-beta molecular sieves by liquid-phase hydrogenatin deoxidation effectively deviate from lignin phenols and
The oxygen-containing functional group such as phenolic monomers and phenol polymer, and then realize the purpose of bio oil upgrading.Liu Shuping by phenol and
The liquid phase alkylation reaction of the tert-butyl alcohol is evaluating the catalysis activity of Beta molecular sieves.As a result show, work as SiO2/Al2O3Than for 15
When, sample due to showing higher catalysis activity with more acidic site and preferable pore passage structure characteristic, Pyrogentisinic Acid
Conversion ratio it is higher, and the selectivity of principal product is higher.Pang Xinmei is with silica alumina ratio (SiO2/Al2O3) it is that 14 Beta molecular sieves are
Catalyst, respectively to gasoline, straight-run diesel oil, heavy oil is catalyzed, and is as a result found, is auxiliary agent in catalytic cracking with Beta molecular sieves
In reaction, the loss of gasoline is advantageously reduced, improve heavy oil conversion ratio and light oil yield, it is also possible to play propylene enhancing, improved
The effect of octane number.JanTo be loaded with the Beta molecular sieves of pt as catalyst, it is explored to pyrolysis oil model
The catalytic hydrogenation of compound and and hydrogenation deoxidation impact.Research finds：Pt-Beta molecular sieves are suitable for the hydrogenation of phenol and add
Hydrogen deoxidation, in the presence of Pt-Beta molecular sieves, phenol is converted into hexamethylene, Hexalin and cyclohexanone mixture, Er Qiesui
The transformation in planta for the increase of silica alumina ratio, cresol and phenol is reduced.Meanwhile, mesoporous point of the synthesis of the laboratory with suitable silica alumina ratio
The Beta molecular sieves of son sieve relatively business are compared, and its catalytic effect has more advantage, and the Hexalin being converted by phenol has higher
Yield.However, the molecular sieve for being catalyzed pyrolysis currently used for coal is single micro porous molecular sieve, its microcellular structure is caused in pyrolysis
Macromole cannot close molecular sieve internal acid active sites so that the catalytic effect of molecular sieve cannot be realized.But introduce be situated between at present
The mode in hole mostly is acidic treatment and alkali process method, and directly roughly, serious possibility saboteur sieves itself to this processing method
Structure and the meso-hole structure duct heterogeneity that formed, therefore catalytic performance and Shape-selective have much room for improvement.At present, using many
There is not been reported for research in terms of level porous molecular sieve participation low-order coal volatiles (pyrolytic tar) situ catalytic modification.
The content of the invention
In order to solve the deficiency existing for above-mentioned prior art, the invention provides a kind of uniform quick, pyrolysis of heat transfer is urged
Change effect good, be capable of achieving to carry out low-order coal middle low-temperature rapid thermal solution, and the coal of situ catalytic modification is carried out to volatiles
Fast pyrogenation couples volatiles situ catalytic modifying apparatus.
Meanwhile, present invention also offers a kind of above-mentioned coal fast pyrogenation couples volatiles situ catalytic modifying apparatus
Realize that pyrolysis catalytic is modified and excellent catalytic effect, pyrolysis rate be fast, tar conversion is high and achievable with reference to multistage porous molecular sieve
The coal fast pyrogenation volatile matters situ catalytic method for modifying of situ catalytic.
The technical scheme that adopted to achieve these goals of the present invention is：
The coal fast pyrogenation coupling volatiles situ catalytic modifying apparatus, including catalytic pyrolysis furnace, catalytic pyrolysis furnace
The pyrolysis travelling oven for making coal heated fast, heat can be moved up and down including being catalyzed stationary furnace and being arranged on above catalysis stationary furnace
Solution travelling oven is coaxially disposed up and down with catalysis stationary furnace, is connected with the outer wall of pyrolysis travelling oven on controllable pyrolysis travelling oven
The elevating mechanism of lower movement；Epimere is provided with catalysis stationary furnace and extends to the reducing connected in pyrolysis travelling oven and with gas circuit
Reactor, reducing reactor includes pyrolysis chamber and the catalytic chamber for connecting from top to bottom, and pyrolysis chamber extends to pyrolysis activity furnace chamber,
Carrier gas inlet is offered at the top of pyrolysis chamber and is connected with helium or nitrogen device by the pipeline installed in carrier gas inlet, be catalyzed
Chamber is arranged on the fixed furnace chamber of catalysis, is provided with for the catalytic bed of the catalyst that paves in catalysis intracavity, opens in catalytic chamber bottom
There is catalytic reforming gas outlet, and be connected with cooling collection device by catalytic reforming gas outlet, in pyrolysis intracavity chamber constant temperature
Area is provided with the Sheng sample basket for holding coal sample.
Further limit, the diameter in the pyrolysis chamber of above-mentioned reducing reactor is 1.5~3 times of catalytic chamber diameter, is pyrolyzed chamber
Length is be catalyzed cavity length 1.5~3 times.
Further limit, on the bottom of above-mentioned Sheng sample basket and side wall air-vent is offered.
Further limit, above-mentioned cooling collection device includes liquid nitrogen cooling bath, receiving flask and closure, receiving flask is placed in
In liquid nitrogen cooling bath, closure is arranged on the bottleneck of receiving flask, offgas outlet is provided with closure and catalytic reforming gas enters
Mouthful.
Further limit, the gas transmission between the catalytic reforming gas access of above-mentioned closure and the outlet of catalytic chamber pyrolysis gas
Heating collar is set with pipeline, and the port of export of gas pipeline extends to receiving flask bottom.
A kind of coal fast pyrogenation realized with above-mentioned coal fast pyrogenation coupling volatiles situ catalytic modifying apparatus
Volatile matters situ catalytic method for modifying, comprises the steps of：
(1) deliming process is carried out to coal with Fluohydric acid. and concentrated hydrochloric acid, is dried 10~12h, transfer in air dry oven afterwards
To vacuum drying oven, 105~110 DEG C, 8~10h is vacuum dried；
(2) weigh and be dried coal sample with quartz sand according to 1：It is placed in agate mortar after 0.5~2 ratio mixing and fully grinds
Mill, makes mix homogeneously, loads and contains sample basket, and adjusts sample basket is contained to the pyrolysis intracavity flat-temperature zone of reducing reactor；
(3) orderly hierarchical porous structure molecular sieve is weighed with quartz sand according to 1：8~10 ratio mix homogeneously is used as catalysis
Agent is filled to the catalysis intracavity of reducing reactor, and the catalytic bed thickness for keeping catalytic chamber is 1~3cm；
(4) after treating that air tight test is good, nitrogen or helium emptying are passed through into reducing reactor, and keep reducing anti-
Answer in device as normal pressure, pyrolysis travelling oven is risen to contain sample basket be dried coal sample top, the pyrolysis temperature of pyrolysis travelling oven is set extremely
The optimal pyrolysis temperature of coal sample, the catalytic temperature of catalysis stationary furnace are 400~900 DEG C, control heating rate scope for 5~120
℃/min；
(5) after the catalytic temperature of catalysis stationary furnace reaches setting value, 1~2h of timing makes catalyst fully activate；
(6) liquid nitrogen is passed through in cooling collection device after activation of catalyst, makes to reach default temperature by elevating mechanism control
The pyrolysis travelling oven of degree drops to original position, is pyrolyzed 20~40min, and the coal sample for making Sheng sample basket is fully pyrolyzed in pyrolysis chamber, pyrolysis
High-temperature gas further situ catalytic modification in catalytic chamber；
(7) after the completion of being pyrolyzed, pyrolysis travelling oven is lifted according to the speed that speed is 55mm/s is lifted, makes reducing reactor
The cooling of pyrolysis chamber, and the gas of situ catalytic modification is collected by liquid nitrogen cooling, completes coal fast pyrogenation volatile matters situ catalytic
Modification.
Further limit, above-mentioned steps (3) weigh orderly hierarchical porous structure molecular sieve with quartz sand according to 1：8~10 ratio
Example mix homogeneously is filled as catalyst and keeps the catalyst of catalytic chamber to pile up formation to the catalysis intracavity of reducing reactor
Catalytic bed thickness is 2cm；Catalyst is 1 with the mass ratio of coal sample:1~10.
Further limit, above-mentioned steps (6) are specifically comprised the steps of：
(6.1) liquid nitrogen is passed through in cooling collection device after activation of catalyst, it is 30ml/min to control gas flow rate, and is protected
Hold in reducing reactor as normal pressure；
(6.2) make the pyrolysis travelling oven for reaching default 600 DEG C of temperature drop to original position by elevating mechanism control, and ensure
Contain sample basket to adjust to the pyrolysis intracavity flat-temperature zone of reducing reactor, be pyrolyzed 30~60min, the coal sample for making Sheng sample basket is fully pyrolyzed,
Solid phase produced by pyrolysis is trapped in Sheng sample basket, and is pyrolyzed the gas phase for producing as carrier gas is moved downwardly into urging for reducing reactor
Change chamber and be fully contacted with catalyst, the macromole volatile matters situ catalytic modification in gas phase.
Compared with prior art, the invention has the beneficial effects as follows：
(1) present invention is independently arranged catalysis stationary furnace and pyrolysis travelling oven, and travelling oven can be moved up and down, and realize coal sample
Quick cooling after the completion of being rapidly heated pyrolysis and pyrolysis, two-part is independently arranged, and stand-alone program temperature control realizes pyrolysis of coal most
The optimal conditionss of big efficiency and catalytic reforming peak efficiency, while being easy to the filling and unloading of catalyst.
(2) present invention collects gaseous product using liquid nitrogen cooling, it is ensured that the abundant condensation of catalytic reforming gas.It is same with this
When, closure seals receiving flask, and the air-tightness of dress device is also ensure that while convenient dismounting so that pyrolytic process essence
But, strong operability.
(3) reducing reactor is present invention employs, by the layout and proportioning raw materials that adjust pyrolysis section and catalytic section, is made
Obtain under conditions of a small amount of catalyst, also can reach effective catalytic effect, reduce catalysis cost, in addition quartz ampoule material is anti-
Device is answered to be easy to observation experiment phenomenon.
(4) selected by the synthesizing ordered hierarchical porous structure molecule of double-template method in situ catalytic method for modifying of the invention
Sieve, the molecular sieve has the advantage of micropore and mesopore molecular sieve concurrently, and catalytic performance is good, heat stability is good, the hole with uniform and ordered
Road structure, mass-transfer efficiency is high, realizes the catalytic reforming of tar macromole, particularly mononuclear aromatics class compound and naphthalene content increases
Plus it is more, overcome the deficiency of conventional molecular sieve.
(5) situ catalytic method for modifying reaction condition of the invention relaxes, and product yield high, quality better are suitable to industrialization
Popularization and application.
Description of the drawings
Fig. 1 is the structural representation that the coal fast pyrogenation of the present invention couples volatiles situ catalytic modifying apparatus.
Fig. 2 is the partial enlarged drawing of catalytic chamber 4 in Fig. 1.
Fig. 3 is the structural representation that collection device 7 is cooled down in Fig. 1.
Fig. 4 is tar with pyrolysis final temperature change curve.
Fig. 5 is semicoke with pyrolysis final temperature change curve.
Fig. 6 is tar with pyrolysis time change curve.
Fig. 7 is the stereoscan photograph of business beta molecular sieve.
Fig. 8 is the stereoscan photograph of multistage porous molecular sieve of the present invention.
Fig. 9 is the transmission electron microscope photo of business beta molecular sieve.
Figure 10 is the transmission electron microscope photo of multistage porous molecular sieve of the present invention.
Figure 11 is multistage porous molecular sieve of the present invention and business beta molecular sieve respectively to low-order coal (god east coal)
The component analyses contrast of gained tar after gained tar and raw coal are pyrolyzed after the catalysis upgrading of volatiles.
Figure 12 is multistage porous molecular sieve of the present invention and business beta molecular sieve respectively to low-order coal (god east coal)
After the catalysis upgrading of volatiles after gained benzene, toluene, the content of BTX and mononuclear aromatics and raw coal pyrolysis obtained by benzene, toluene,
The content balance of BTX and mononuclear aromatics.
Figure 13 multistage porous molecular sieves of the present invention are with business beta molecular sieve respectively to low-order coal (god east coal) heat
The selectivity contrast of gained PC and mononuclear phenolic after gained PC and mononuclear phenolic are pyrolyzed with raw coal after the catalysis upgrading of solution volatile matters.
Specific embodiment
Technical scheme is further described in conjunction with drawings and Examples, but the present invention is not limited only to
Following implementation situations.
Referring to Fig. 1, the coal fast pyrogenation coupling volatiles situ catalytic modifying apparatus of the present invention are by pyrolysis activity
Stove 1, catalysis stationary furnace 2, elevating mechanism 5, reducing reactor, Sheng sample basket 6, helium or nitrogen device and cooling collection device 7
Combination is constituted.
Wherein, travelling oven 1 and the catalysis composition catalytic pyrolysis furnace of stationary furnace 2 are pyrolyzed, antipyretic, the catalytic reforming of coal sample is realized,
Using the heating of open type single hop, digital process controlling temp type heating furnace, pyrolysis travelling oven 1 and catalysis stationary furnace 2 erect row and are coaxially disposed, and urge
Change stationary furnace 2 to fix in lower section, the outer wall for being pyrolyzed travelling oven 1 is connected by connector with elevating mechanism 5, by elevating mechanism 5
Adjusting pyrolysis travelling oven 1 can move up and down, and its hoisting depth scope is 0-550mm, and liftings speed is 55mm/s, and pyrolysis activity
The length of stove 1 is 500~800mm, and internal diameter is 10~100mm, and length is be catalyzed the length of stationary furnace 2 1~3 times, and internal diameter is to urge
Change the internal diameter of stationary furnace 2 2~5 times, can need to adjust the distribution proportion of its length and internal diameter according to pyrolysis.Fix in catalysis
The inner chamber of stove 2 is embedded with reducing reactor, and the reducing reactor adopts quartz material, and the temperature range that can be born is room temperature~950
DEG C, reducing reactor includes pyrolysis chamber 3 and the catalytic chamber 4 for connecting from top to bottom, and the length of catalytic chamber 4 is 360mm, and internal diameter is
10mm, is sleeved on the catalysis inner chamber of stationary furnace 2, is coaxially disposed with catalysis stationary furnace 2, the diameter and the diameter of catalytic chamber 4 in chamber pyrolysis chamber 3
Can be 1.5~3：Adjustment in 1 proportion, the pyrolysis length of chamber 3 is that the length of catalytic chamber 4 also can be 1.5~3：1 proportion
Interior adjustment, it can need according to the specification and pyrolysis catalytic reaction of outside pyrolysis travelling oven 1 and catalysis stationary furnace 2 and adjust.
The catalytic bed 8 for the catalyst that paves is fixed with the catalytic chamber 4, in catalytic bed 8 can catalyst filling, referring to Fig. 2, catalysis
Bed 8 is made up of stay tube 8-1, sieve plate 8-2 and silica wool layer 8-3, and stay tube 8-1 is fixed on the bottom of catalytic chamber 4, for supporting
Sieve plate 8-2, making the volatile matters of pyrolysis can effectively stop in catalytic bed 8, on sieve plate 8-2 and catalyst upper surface is covered
There is silica wool 8-3, catalyst can be paved between upper and lower silica wool 8-3, the silica wool 8-3 above catalyst can be used to disperse
Air-flow so that volatiles can be uniformly through catalyst, and the silica wool 8-3 below catalyst can effectively prevent catalyst from leading to
Cross sieve plate 8-2 and drain to the bottom of catalytic chamber 4, while can play a part of to filter reacting gas so that gas is uniform after catalytic reforming
Through silica wool 8-3 and sieve plate 8-2 mesh, collect in the bottom of catalytic chamber 4.Catalytic reforming gas is provided with the bottom of catalytic chamber 4
Outlet, is connected by screw thread squash type stainless steel coil with cooling collection device 7；Pyrolysis chamber 3 is, in the top of catalytic chamber 4, to extend to
In pyrolysis travelling oven 1, its length is 740mm, and internal diameter is 20mm, and the top for being pyrolyzed chamber 3 offers carrier gas inlet, is squeezed by screw thread
Pressure type stainless steel coil is connected with the gas outlet of helium or nitrogen device, helium or nitrogen can be introduced in reducing reactor.In heat
Flat-temperature zone is also mounted with a Sheng sample basket 6 for holding coal sample in solution chamber 3, on the bottom of the Sheng sample basket 6 and side wall
It is furnished with 4 row air-vents, it is ensured that the solid retention that pyrolysis is produced, gas flows through air-vent.
Wherein, the amount for containing coal sample in sample basket 6 is relevant with the catalytic amount in catalytic chamber 4, however, to ensure that preferably urging
Change effect and control catalyst amount, the thickness of the catalytic bed that the catalyst of the present embodiment is constituted is 1~3cm, with 2cm
It is preferred.
Need it is further noted that above-mentioned elevating mechanism 5 can adopt conventional hydraulicefficiency elevation structure 5, vertical silk
Bar elevating mechanism 5, chain-type elevating mechanism 5, gear-rack type lifter structure 5 etc..
Need it is further noted that referring to Fig. 3, above-mentioned cooling collection device 7 is by liquid nitrogen cooling bath 7-1, collects
Bottle 7-2 and closure 7-4, receiving flask 7-2 are placed in liquid nitrogen cooling bath 7-1, and by liquid nitrogen gas in receiving flask 7-2 is cooled down,
Closure 7-4 is arranged on the bottleneck of receiving flask 7-2, and offgas outlet and catalytic reforming gas access are provided with closure 7-4,
Connected with the catalytic reforming gas outlet of catalytic chamber 4 by catalytic reforming gas access, in order to ensure catalytic reforming gas from urging
Change chamber 4 to be out incubated afterwards, the gas pipeline 7- between catalytic reforming gas access and the catalytic reforming gas outlet of catalytic chamber 4
Heating collar 7-5 is set with 3, and the port of export of gas pipeline 7-3 extends to the bottom of receiving flask 7-2, catalytic reforming High Temperature Gas
Body is quenched in receiving flask 7-2, makes condensation effect more preferable.
Need it is further noted that the pyrolysis chamber 3 of above-mentioned reducing reactor and the capacity distribution of catalytic chamber 4 are conducive to heat
The regulation of solution section and catalytic section proportioning raw materials so that effective catalytic effect is also capable of achieving under conditions of a small amount of catalyst, because
This, the diameter in the pyrolysis chamber 3 of the present invention is 1.5~3 times of the diameter of catalytic chamber 4, and the pyrolysis length of chamber 3 is the 1.5 of the length of catalytic chamber 4
~3 times, can be adjusted according to actual treatment amount in this proportion.
The coal fast pyrogenation volatilization realized with above-mentioned coal fast pyrogenation coupling volatiles situ catalytic modifying apparatus
Divide situ catalytic method for modifying, be to comprise the steps of：
(1) deliming process is carried out to coal with Fluohydric acid. and concentrated hydrochloric acid, is dried 10~12h, transfer in air dry oven afterwards
To vacuum drying oven, 105~110 DEG C, 8~10h is vacuum dried；
(2) weigh and be dried coal sample with quartz sand according to 1：It is placed in agate mortar after 0.5~2 ratio mixing and fully grinds
Mill, makes mix homogeneously, loads and contains sample basket 6, and adjusts sample basket 6 is contained to flat-temperature zone in the pyrolysis chamber 3 of reducing reactor；
(3) three-dimensional order hierarchical porous structure molecular sieve is weighed with quartz sand according to 1：8~10 ratio mix homogeneously conduct
Catalyst is filled to the catalytic chamber 4 of reducing reactor, and the catalytic bed thickness for keeping catalytic chamber 4 is 1~3cm；Catalyst with
The mass ratio of coal sample is 1:1~10.
(4) the pyrolysis chamber 3 of reducing reactor is connected with helium or nitrogen device, catalytic chamber 4 connects with cooling collection device 7
Connect, after the completion of connection, helium or nitrogen, the air-tightness of verifying attachment are passed through in reducing reactor, it is ensured that the air-tightness of device
Well, and keep in reducing reactor as normal pressure, control gas flow rate for 30ml/min, travelling oven 1 will be pyrolyzed afterwards and rises to Sheng
Sample basket 6 is dried coal sample top, and the optimal pyrolysis temperature for arranging the pyrolysis temperature to coal sample of pyrolysis travelling oven 1 is 600 DEG C, catalysis
The catalytic temperature of stationary furnace 2 is 400~900 DEG C, controls heating rate scope for 5~120 DEG C/min；
(5) after the catalytic temperature of catalysis stationary furnace 2 reaches setting value, 1~2h of timing makes catalyst fully activate；
(6) coal sample pyrolysis, is specifically realized by following steps：
(6.1) it is passed through liquid nitrogen in cooling collection device 7 after activation of catalyst；
(6.2) the pyrolysis travelling oven 1 of the optimum temperature for reaching default 600 DEG C is made to drop to original by the control of elevating mechanism 5
Position, and ensure that containing sample basket 6 adjusts to flat-temperature zone in the pyrolysis chamber 3 of reducing reactor, is pyrolyzed 10~60min, preferably 20~
40min, the coal sample for making Sheng sample basket 6 is fully pyrolyzed, and solid phase produced by pyrolysis is trapped in Sheng sample basket 6, and be pyrolyzed the gas phase that produces with
Carrier gas to be moved downwardly into the catalytic chamber 4 of reducing reactor and be fully contacted with catalyst, the macromole volatile matters in gas phase
Situ catalytic is modified.
(7) after the completion of being pyrolyzed, pyrolysis travelling oven 1 is lifted according to the speed that speed is 55mm/s is lifted, makes reducing reactor
Pyrolysis chamber 3 lower the temperature, and situ catalytic modification gas by liquid nitrogen cooling collection.
Above-mentioned orderly hierarchical porous structure molecular sieve is using known double-template method (organic silicon surfactant TPOAC
With small molecule quaternary ammonium salt TEAOH) prepare multi-stage porous beta molecular sieves (Beta)
In order to verify the present invention technique effect, applicant done it is substantial amounts of verified, now with it is following test be
Example is illustrated.
(1) it is pyrolyzed optimum process condition
In order to preferably explore pyrolytical condition to being pyrolyzed the impact of yield, inventor is to being pyrolyzed the time of staying and pyrolysis temperature
Two process conditions, pyrolysis step is consistent with the step in the mode of embodiment 1.Test respectively by independent variable of pyrolysis temperature
450 DEG C, 500 DEG C, 550 DEG C, 560 DEG C, 570 DEG C, 580 DEG C, 590 DEG C, 600 DEG C, 650 DEG C of some shadows of row temperature to tar yield
Ring, and under 600 DEG C of optimum temperatures, with the time of staying as independent variable, test respectively 10min, 20min, 30min, 40min,
Impacts of the 50min to tar yield, draws most optimal retention time.Referring to Fig. 4~6.
Show with reference to Fig. 4~6 result：With the rising of pyrolysis temperature, tar yield increases, to tar yield when 600 DEG C
Maximum is reached, tar yield is 15.77%, after 600 DEG C, with the rising of temperature, tar yield is gradually reduced；Semicoke is produced
Amount declines with the rising of pyrolysis temperature；With the increase of pyrolysis time, tar yield is presented the trend of increase, reaches during 30min
To maximum 14.9%；After 30min, tar yield is drastically reduced.In consideration of it, determining that this pyrolysis reactor is directed to low order pyrolysis of coal
Obtain tar best operating condition be：600 DEG C of pyrolysis temperature, pyrolysis time 30min, elevator furnace realizes room temperature to 600 DEG C
Heating rate is about 150 DEG C/min.
(2) morphology analysis of multistage porous molecular sieve and business beta molecular sieve
Multi-stage porous beta is prepared using double-template method (organic silicon surfactant TPOAC and small molecule quaternary ammonium salt TEAOH)
Molecular sieve (Beta), and multi-stage porous beta molecular sieves (Beta) and business beta molecular sieve (Nankai's catalyst plant) have been carried out it is right
Than analysis (two kinds of samples are in ion exchange and calcination processing with the conditions of), can from stereoscan photograph Fig. 7 and 8 contrasts
Go out, two kinds of zeolite crystal sizes quite, are 200-500nm, and wherein multi-stage porous beta sieve particles are relatively decentralized, without substantially
Agglomeration, and business beta molecular sieve then shows more obvious agglomeration；Can be with from transmission electron microscope photo Fig. 9 and 10
Find out, two kinds of molecular sieves are respectively provided with higher crystalline state, wherein there is transgranular big mesopore in multi-stage porous Beta zeolite crystals, and
Business beta molecular sieve is simple micro-pore zeolite.
(3) different catalysts are used to be pyrolyzed Contrast on effect in the catalytic reforming of low-order coal (god east coal) volatiles
Working condition：600 DEG C of 1 pyrolysis temperature of pyrolysis travelling oven, pyrolysis time 30min, 150 DEG C/min of heating rate；Urge
Change 450 DEG C of the catalytic reforming temperature of stationary furnace 2, molecular sieve catalyst loadings 0.2g, 40-60 mesh, after uniform mixing quartz sand
Bed height 2cm；Coal sample loads 1g；He atmosphere, flow velocity 30ml/min；Product tar 2.4ml methanol quantitative collections；GC-MC
Detection.
The tar after the pyrolysis of tar (methanol soluble thing) constituent species and raw coal after two kinds of molecular sieve catalytic upgradings
Comparative, referring to Figure 11,12 and 13.
Contrasted from Figure 11, in the tar after the molecular sieve catalytic upgrading of business beta, benzene,toluene,xylene contains
Amount is compared compared with raw coal and respectively reduce 8.92%, 1.43% and 13.34%, and total xylene content reduces 8.92%, except BTX
Outer mononuclear aromatics total amount then improves 4.31%.And the tar after multi-stage porous Beta molecular sieve catalytic upgradings of the present invention
In, benzene, toluene, the content of dimethylbenzene and mononuclear aromatics is compared compared with raw coal and increase respectively 1.72%, 21.41%, 5.30%,
16.71%, and the content of dimethylbenzene is compared compared with raw coal and reduces 9.64%.Analyze its reason essentially consist in it is used in the present invention
Multi-stage porous Beta molecular sieves have more preferable acid catalysis, and good duct transmission advantage, are conducive to connecting on carbon
Aromatic hydrocarbon comes off and the de- alkyl of dimethylbenzene obtains toluene.
Contrasted from Figure 12, in the tar after the molecular sieve catalytic upgrading of business beta, phenol, cresol, phenols chemical combination
Thing compared with raw coal in compare and reduce 24.51%, 41.61%, 36.26%；After multi-stage porous Beta molecular sieve catalytic upgradings
Tar in, phenol, cresol, phenolic compound in turn reduce 43.04%, 50.78%, 52.26%.And it is of the invention using multistage
The phenol decomposition effect of hole Beta molecular sieves is more excellent, demonstrates again that the more suitable catalysis of multi-stage porous Beta molecular sieves is acid and multistage
Transmit advantage in duct.
Contrasted from Figure 13, in the tar after the molecular sieve catalytic upgrading of business beta, the homologue of naphthalene and naphthalene compared with
298.28%, alkane is improve in raw coal and reduces 92.27%；Tar after multi-stage porous Beta molecular sieve catalytic upgradings
In, the homologue of naphthalene and naphthalene reduces 89.80% compared with 323.48%, alkane is improve in raw coal, analyze its reason essentially from
Act in the aromatisation of beta molecular sieves so that the alkane derivative in volatile matters occurs aromatisation, hence in so that monocyclic virtue
The increase of hydrocarbon compound, the increase of naphthalene content may be from the polycondensation reaction in aromatic hydrocarbons and phenols.While the product of the present invention
The macromole condensed-nuclei aromatics such as more naphthalenes, anthracene, phenanthrene is detected in thing tar, illustrates multi-stage porous Beta molecular sieves compared to business
Beta molecular sieves, with more preferable mass-transfer efficiency.
In sum, process choice multi-stage porous Beta molecular sieves of the invention as catalytic reforming catalyst, to tar
The content of middle benzene,toluene,xylene and mononuclear aromatics is compared compared with raw coal, and content is higher, phenol, cresol, content of phenolic compounds drop
Low, the homologue of naphthalene and naphthalene is improved, and Determination of Alkane Content is reduced, with business beta molecular sieve as catalytic reforming catalyst phase
Than both effects are similar, but multi-stage porous beta molecular sieve effects are more significantly, and the multi-stage porous of the present invention are also illustrated simultaneously
Beta molecular sieves combine the technique of the present invention, make mass-transfer efficiency higher, and catalytic reforming effect is more preferable.
Claims (8)
1. a kind of coal fast pyrogenation couples volatiles situ catalytic modifying apparatus, including catalytic pyrolysis furnace, it is characterised in that：
The catalytic pyrolysis furnace includes catalysis stationary furnace (2) and is arranged on to be moved up and down above catalysis stationary furnace (2) to make coal fast
The pyrolysis travelling oven (1) that speed is heated, pyrolysis travelling oven (1) is coaxially disposed up and down with catalysis stationary furnace (2), in pyrolysis travelling oven
(1) elevating mechanism (5) that controllable pyrolysis travelling oven (1) moves up and down is connected with outer wall；Set in catalysis stationary furnace (2)
It is equipped with epimere and extends to the reducing reactor for connecting in pyrolysis travelling oven (1) and with gas circuit, reducing reactor is included from top to bottom
The pyrolysis chamber (3) of connection and catalytic chamber (4), pyrolysis chamber (3) extends to pyrolysis travelling oven (1) inner chamber, opens at the top of pyrolysis chamber (3)
It is provided with carrier gas inlet and is connected with helium or nitrogen device by the pipeline installed in carrier gas inlet, catalytic chamber (4) is arranged on urges
Change stationary furnace (2) inner chamber, the catalytic bed (8) for the catalyst that paves is provided with catalytic chamber (4), catalytic chamber (4) bottom is opened
There is catalytic reforming gas outlet, and be connected with cooling collection device (7) by catalytic reforming gas, it is permanent in pyrolysis chamber (3) inner chamber
Warm area is provided with Sheng sample basket (6) for holding coal sample.
2. coal fast pyrogenation according to claim 1 couples volatiles situ catalytic modifying apparatus, it is characterised in that：
The diameter in the pyrolysis chamber (3) of the reducing reactor is 1.5~3 times of catalytic chamber (4) diameter, and pyrolysis chamber (3) length is catalysis
1.5~3 times of chamber (4) length.
3. coal fast pyrogenation according to claim 1 couples volatiles situ catalytic modifying apparatus, it is characterised in that：
Air-vent is offered on the bottom of Sheng sample basket (6) and side wall.
4. coal fast pyrogenation according to claim 1 couples volatiles situ catalytic modifying apparatus, it is characterised in that：
Cooling collection device (7) is including liquid nitrogen cooling bath (7-1), receiving flask (7-2) and closure (7-4), receiving flask (7-2)
It is placed in liquid nitrogen cooling bath (7-1), closure (7-4) is arranged on the bottleneck of receiving flask (7-2), is provided with closure (7-4)
Offgas outlet and catalytic reforming gas access.
5. coal fast pyrogenation according to claim 4 couples volatiles situ catalytic modifying apparatus, it is characterised in that：
Gas pipeline (the 7- being connected between the catalytic reforming gas access of the closure (7-4) and the outlet of catalytic chamber (4) pyrolysis gas
3) heating collar (7-5) is set with, and the port of export of gas pipeline (7-3) extends to receiving flask (7-2) bottom.
6. the coal that the coal fast pyrogenation coupling volatiles situ catalytic modifying apparatus described in a kind of use claim 1 are realized is fast
Fast volatiles situ catalytic method for modifying, it is characterised in that comprise the steps of：
(1) deliming process is carried out to coal with Fluohydric acid. and concentrated hydrochloric acid, is dried 10~12h in air dry oven afterwards, shift the most pure virginity
Empty drying baker, is vacuum dried 8~10h by 105~110 DEG C；
(2) weigh and be dried coal sample with quartz sand according to 1：It is placed in agate mortar after 0.5~2 ratio mixing and is fully ground, makes
Mix homogeneously, loads and contains sample basket (6), and Sheng sample basket (6) is adjusted to the interior flat-temperature zone in pyrolysis chamber (3) of reducing reactor；
(3) orderly hierarchical porous structure molecular sieve is weighed with quartz sand according to 1：8~10 ratio mix homogeneously is filled out as catalyst
It is charged in the catalytic chamber (4) of reducing reactor, the catalytic bed thickness of holding catalytic chamber (4) is 1~3cm；
(4) after treating that air tight test is good, nitrogen or helium emptying are passed through into reducing reactor, controlling gas flow rate is
30ml/min, and keeping in reducing reactor as normal pressure, pyrolysis travelling oven (1) is risen to contain sample basket (6) be dried coal sample top,
It is 400 to arrange the optimal pyrolysis temperature of the pyrolysis temperature to coal sample of pyrolysis travelling oven (1), the catalytic temperature of catalysis stationary furnace (2)
~900 DEG C, heating rate scope is controlled for 5~120 DEG C/min；
(5) after the catalytic temperature of catalysis stationary furnace 2 reaches setting value, 1~2h of timing makes catalyst fully activate；
(6) liquid nitrogen is passed through in cooling collection device (7) after activation of catalyst, makes to reach by elevating mechanism (5) control default
The pyrolysis travelling oven (1) of temperature drops to original position, is pyrolyzed 10~60min, makes the coal sample of Sheng sample basket (6) abundant in pyrolysis chamber (3)
Pyrolysis, high-temperature gas further situ catalytic modification in catalytic chamber (4) of pyrolysis；
(7) after the completion of being pyrolyzed, pyrolysis travelling oven (1) is lifted according to the speed that speed is 55mm/s is lifted, makes reducing reactor
Pyrolysis chamber (3) cooling, and the gas of situ catalytic modification is collected by liquid nitrogen cooling, is completed coal fast pyrogenation volatile matters original position and is urged
Change modification.
7. coal fast pyrogenation volatile matters situ catalytic method for modifying according to claim 6, it is characterised in that the step
(3) orderly hierarchical porous structure molecular sieve is weighed with quartz sand according to 1：8~10 ratio mix homogeneously as catalyst fill to
In the catalytic chamber (4) of reducing reactor, keeping the catalyst of catalytic chamber (4), to pile up the catalytic bed thickness of formation be 2cm；Urge
Agent is 1 with the mass ratio of coal sample:1~10.
8. coal fast pyrogenation volatile matters situ catalytic method for modifying according to claim 6, it is characterised in that the step
(6) specifically comprise the steps of：
(6.1) it is passed through liquid nitrogen in cooling collection device (7) after activation of catalyst；
(6.2) make the pyrolysis travelling oven (1) for reaching default 600 DEG C of temperature drop to original position by elevating mechanism (5) control, and protect
Card is contained sample basket (6) and is adjusted to the interior flat-temperature zone in pyrolysis chamber (3) of reducing reactor, is pyrolyzed 20~40min, makes the coal of Sheng sample basket (6)
Sample is fully pyrolyzed, and solid phase produced by pyrolysis is trapped in Sheng sample basket (6), and is pyrolyzed the gas phase for producing as carrier gas is moved downwardly into
The catalytic chamber (4) of reducing reactor is simultaneously fully contacted with catalyst, the macromole volatile matters situ catalytic modification in gas phase.
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| CN108913177A (en) * | 2018-07-12 | 2018-11-30 | 中国科学院上海高等研究院 | A kind of method and device of the biomass pyrolytic tar low temperature removing based on microwave hot spot |
| CN108913179A (en) * | 2018-08-31 | 2018-11-30 | 西北大学 | A kind of directional catalyzing cracker and technique |
| CN109437227A (en) * | 2018-11-30 | 2019-03-08 | 西北大学 | A kind of preparation method of Ga containing zeolite and the application in the modification of pyrolysis of coal volatile matter |
| CN110208451A (en) * | 2019-04-26 | 2019-09-06 | 合肥工业大学 | Bipolar micro fixed-bed reactor combination Photoionization Mass Spectrometry on-line detecting system and method |
| CN110484286A (en) * | 2019-09-02 | 2019-11-22 | 哈尔滨工业大学 | Pyrolysis gas deposits the method that carbon and tar processed inhibit in a kind of high volatile coal thermal conversion processes |
| CN110713843A (en) * | 2019-10-14 | 2020-01-21 | 江苏海洋大学 | Coal and biomass co-pyrolysis reaction device and method |
| CN112159685A (en) * | 2020-09-16 | 2021-01-01 | 中国科学院广州能源研究所 | Reaction system and method for realizing in-situ and non-in-situ catalytic fast pyrolysis gasification of organic solid waste |
| CN113101874A (en) * | 2021-04-21 | 2021-07-13 | 华中科技大学 | Closed U-shaped tube reactor and control method thereof |
| CN113908789A (en) * | 2020-07-09 | 2022-01-11 | 国家能源投资集团有限责任公司 | Pyrolysis reactor |
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| CN108913177A (en) * | 2018-07-12 | 2018-11-30 | 中国科学院上海高等研究院 | A kind of method and device of the biomass pyrolytic tar low temperature removing based on microwave hot spot |
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| CN108913179B (en) * | 2018-08-31 | 2024-01-16 | 西北大学 | Directional catalytic cracking device and process |
| CN109437227B (en) * | 2018-11-30 | 2022-03-15 | 西北大学 | Preparation method of gallium-containing zeolite and application of gallium-containing zeolite in coal pyrolysis volatile modification |
| CN109437227A (en) * | 2018-11-30 | 2019-03-08 | 西北大学 | A kind of preparation method of Ga containing zeolite and the application in the modification of pyrolysis of coal volatile matter |
| CN110208451A (en) * | 2019-04-26 | 2019-09-06 | 合肥工业大学 | Bipolar micro fixed-bed reactor combination Photoionization Mass Spectrometry on-line detecting system and method |
| CN110208451B (en) * | 2019-04-26 | 2022-05-24 | 合肥工业大学 | Online detection system and method for bipolar miniature fixed bed reactor combined with photoionization mass spectrometry |
| CN110484286A (en) * | 2019-09-02 | 2019-11-22 | 哈尔滨工业大学 | Pyrolysis gas deposits the method that carbon and tar processed inhibit in a kind of high volatile coal thermal conversion processes |
| CN110713843A (en) * | 2019-10-14 | 2020-01-21 | 江苏海洋大学 | Coal and biomass co-pyrolysis reaction device and method |
| CN110713843B (en) * | 2019-10-14 | 2021-05-11 | 江苏海洋大学 | Coal and biomass co-pyrolysis reaction device and method |
| CN113908789A (en) * | 2020-07-09 | 2022-01-11 | 国家能源投资集团有限责任公司 | Pyrolysis reactor |
| CN113908789B (en) * | 2020-07-09 | 2023-06-30 | 国家能源投资集团有限责任公司 | Pyrolysis reactor |
| CN112159685A (en) * | 2020-09-16 | 2021-01-01 | 中国科学院广州能源研究所 | Reaction system and method for realizing in-situ and non-in-situ catalytic fast pyrolysis gasification of organic solid waste |
| CN113101874A (en) * | 2021-04-21 | 2021-07-13 | 华中科技大学 | Closed U-shaped tube reactor and control method thereof |
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