CN108913179A - A kind of directional catalyzing cracker and technique - Google Patents
A kind of directional catalyzing cracker and technique Download PDFInfo
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- CN108913179A CN108913179A CN201811013130.3A CN201811013130A CN108913179A CN 108913179 A CN108913179 A CN 108913179A CN 201811013130 A CN201811013130 A CN 201811013130A CN 108913179 A CN108913179 A CN 108913179A
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- 238000000034 method Methods 0.000 title abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 129
- 238000006243 chemical reaction Methods 0.000 claims abstract description 120
- 239000007789 gas Substances 0.000 claims abstract description 89
- 239000003245 coal Substances 0.000 claims abstract description 80
- 239000002994 raw material Substances 0.000 claims abstract description 72
- 239000012495 reaction gas Substances 0.000 claims abstract description 57
- 238000000197 pyrolysis Methods 0.000 claims abstract description 46
- 239000002028 Biomass Substances 0.000 claims abstract description 33
- 150000003254 radicals Chemical class 0.000 claims abstract description 30
- 238000007233 catalytic pyrolysis Methods 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 23
- 230000004913 activation Effects 0.000 claims abstract description 16
- 230000009471 action Effects 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 157
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 86
- 239000012159 carrier gas Substances 0.000 claims description 78
- 230000004907 flux Effects 0.000 claims description 53
- 238000009826 distribution Methods 0.000 claims description 44
- 239000007787 solid Substances 0.000 claims description 35
- 238000003860 storage Methods 0.000 claims description 24
- 239000008246 gaseous mixture Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 230000003213 activating effect Effects 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 238000005336 cracking Methods 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 230000001276 controlling effect Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001514 detection method Methods 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 claims description 7
- 239000012263 liquid product Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 abstract description 26
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000011269 tar Substances 0.000 description 91
- 230000033228 biological regulation Effects 0.000 description 36
- 240000008042 Zea mays Species 0.000 description 28
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 28
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 28
- 235000005822 corn Nutrition 0.000 description 28
- 239000010907 stover Substances 0.000 description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 17
- 229910052593 corundum Inorganic materials 0.000 description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 description 13
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 238000004523 catalytic cracking Methods 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 239000011280 coal tar Substances 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 239000000571 coke Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000000875 corresponding effect Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 230000037452 priming Effects 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- -1 Small molecule free radical Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229960004424 carbon dioxide Drugs 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 150000001896 cresols Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/04—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
- C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
-
- 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
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
A kind of directional catalyzing cracker and technique, reaction atmosphere in the reaction tube of upper section furnace, which tiles by first gas distributor to catalyst bed, carries out the activation of reaction gas, reaction atmosphere is under the action of catalyst, it generates free radicals, free radical is contacted with the free radical that the raw material pyrolysis in raw material bed generates, obtained gaseous products tile by third gas distributor to catalyst A bed, catalyst A bed carries out catalytic pyrolysis to the gaseous products of pyrolytic reaction, product after catalytic pyrolysis enters catalyst B bed and carries out shape selective catalysis, product after shape selective catalysis enters condensing unit and is condensed, obtained tar liquid.The raw materials such as coal, biomass are pyrolyzed to improve tar yield process and orient corresponding product distributed process and be integrated into a set of technique by the present invention, simplify integrated artistic process, it is environmentally friendly, reduce Energy Consumption Cost, improve production efficiency, and it is easy to mass production scale, it is suitable for industrial application.
Description
Technical field
The invention belongs to field of energy and chemical technology, it is related to a kind of directional catalyzing cracker and technique.
Background technique
Pyrolysis of coal is the committed step of coal trans-utilization, the technical process such as burning of coal, gasification, liquefaction will occur or
Undergo pyrolytic process.But coal tar low yield, heavy components content height, and heavy group again that traditional pyrolysis of coal obtains
Point have the characteristics that higher boiling, high viscosity, separation are difficult, in target product all kinds of products distributions in a jumble and also relative amount compared with
It is low, therefore all kinds of products cannot be effectively enriched with.
Biomass is mainly made of cellulose, hemicellulose, lignin etc., and pyrolysis is also biomass thermal chiral process
In most basic process, be the synthesis of its liquefaction, gasification and combustion process, due to three big cellulose contents in different biomass materials
Difference, so there are larger difference, Bu Nengjin for the content for the bio oil that biomass pyrolysis process generates, ingredient and product distribution
Row effectively further directly utilizes.
Therefore, the pyrolytic tars yields such as coal, biomass, orientation regulation tar product distribution, so that target tar produces are improved
The upgrading of article matter, generating has high added value tar product, to the efficient of China's coal chemical industry, Biochemical Industry and national energy
Using with important and profound significance.
Pyrolysis of coal acquisition tar yield is low, is limited by low hydrogen-carbon ratio in coal.During pyrolysis of coal, dividing greatly in texture of coal
The continuous depolymerization of minor structure, the macromolecular radical being variously formulated, hydroperoxyl radical etc..Studies have shown that burnt during pyrolysis of coal
The formation of oil is related by thermal cracking and the cracking stabilization of free radical with organic macromolecule in coal.Excessive cracking is possible to will form
The combination of gaseous product, free radical and small molecule is likely to form tar, and the combination between free radical is likely to form tar,
Macromolecular may be re-formed to exist in the form of solid semicoke.Therefore, during pyrolysis of coal, hydrogen-rich is applied by outside
Small molecule free radical, so that the free radical that coal cracking generates is stablized, it is the effective way for improving tar yield.
High hydrogen price, so that the raw materials such as coal, biomass pass through hydropyrolysis, to improve the pyrolysis coke of corresponding raw material
Yield and the quality cost with higher of oil, constrain their practicability.Methane is the main component of natural gas, and source is wide
It is general, possess high hydrogen-to-carbon ratio, and cheap, be ideal hydrogen-rich gas, therefore can be using methane as coal, life
The reaction atmosphere of the raw materials such as substance pyrolysis.But the study found that 800 DEG C hereinafter, methane does not react substantially with coal, first
Alkane is equivalent to inert atmosphere in pyrolytic process, can not improve coal tar oil yield because methane under the conditions of non-catalytic very
Stablize and is difficult to activate.
Pyrolysis of coal forms tar product, and heavy components content is higher, and oxygenatedchemicals is more, so tar low quality.
Therefore regulation is oriented to pyrolysis of coal tar, then can get higher yields has high added value target product.
Currently, improve coal, the raw materials pyrolytic tar yield such as biomass and to the raw materials pyrolytic tar product such as coal, biomass into
Row orientation regulation, generally all carries out in two sets independent systems respectively, result in this way integrated artistic complication, energy consumption at
This height, the problems such as product utilization rate is low, production efficiency is low.Using both ends formula fixed bed, the raw materials such as coal, biomass heat is improved
While solving tar yield, shape selective catalysis can be also carried out to the raw materials pyrolytic tar product such as coal, biomass, and then it is burnt to orient regulation
The device and method of oil product are but rarely reported.
Summary of the invention
In order to overcome the problems of the above-mentioned prior art, the object of the present invention is to provide a kind of cracking of directional catalyzing
Device and technique while can be improved the raw materials pyrolytic tar products collection efficiency such as coal, biomass, can also orient regulation coal, life
The distribution of the raw materials pyrolytic tar product such as substance, to obtain the dreamboat tar product with high added value.
To achieve the goals above, used technical solution is as follows by the present invention：
A kind of directional catalyzing cracker, including feeder, for improve pyrolysis of coal reaction tar yield upper section furnace,
For carrying out the lower section furnace, cooling device and temperature and pressure control device that type is selected in catalysis to pyrolytic tar；Upper section furnace and
Lower section furnace is cylindrical body, and two sections of upper section furnaces and lower section furnace are coaxial up and down, and center vertical is arranged in upper section furnace and lower section furnace
There is reaction tube；Feeder is connected with upper section furnace, and feeder, upper section furnace and lower section furnace are filled with temperature and pressure controller
It sets connected；Cooling device is arranged below lower section furnace.
A further improvement of the present invention lies in that feeder include the first carrier gas bottle, the second carrier gas bottle, third carrier gas bottle,
First carrier gas flux control valve, the second carrier gas flux control valve, third carrier gas flux control valve, mixed gas tank and for regulating and controlling
The total carrier gas flux controller of the system of the total flow of reaction gas；Outlet the first carrier gas flux control valve of first carrier gas bottle and mixed
It closes gas tank entrance to be connected, outlet the second carrier gas flux control valve of the second carrier gas bottle is connected with mixed gas tank entrance, and third carries
The outlet of gas cylinder is connected through third carrier gas flux control valve with mixed gas tank entrance, and mixed gas tank is exported through the total carrier gas flux of system
Controller is connected with upper section furnace entrance.
A further improvement of the present invention lies in that temperature and pressure control device includes the first carrier gas flux controller, the
Two carrier gas flux controllers, third carrier gas flux controller, upper section furnace middle portion temperature controller, the control of upper section furnace upper temp
Under device, upper section furnace temperature of lower controller, lower section furnace middle portion temperature controller, lower section furnace upper temp controller and lower section furnace
Portion's temperature controller；First carrier gas flux controller is connected with the first carrier gas flux control valve, the second carrier gas flux controller with
Second carrier gas flux control valve is connected, and third carrier gas flux controller is connected with third carrier gas flux control valve；The furnace of upper section furnace
The external position of upper, middle and lower three, is separately connected upper section furnace middle portion temperature control of the signal wire into temperature and pressure control device
Device processed, upper section furnace upper temp controller, upper section furnace temperature of lower controller, the outer portion of upper, middle and lower three of the furnace body of lower section furnace
Position, is separately connected signal wire to lower section furnace middle portion temperature controller, lower section furnace upper temp controller, lower section furnace temperature of lower control
Device processed.
A further improvement of the present invention lies in that in reaction tube in upper section furnace, from top to bottom equipped with gas distributor, catalysis
Agent bed, the first solids distribution device, raw material bed, the second solids distribution device and second gas distributor；Wherein, gas is distributed
For device for making reaction gas uniformly be distributed in catalyst bed, catalyst bed is used for activating reaction gas, the first solids distribution device
It is respectively used to tiling catalyst bed and raw material bed with the second solids distribution device, second gas distributor is for making pyrolytic reaction
Gaseous product stream afterwards is into the reaction tube of lower section furnace.
A further improvement of the present invention lies in that in reaction tube in lower section furnace, from top to bottom equipped with third gas distributor,
Catalyst A bed, third solids distribution device, catalyst B bed, the 4th solids distribution device and the 4th gas distributor；Wherein,
Third gas distributor is for the gaseous product distribution after making pyrolytic reaction in catalyst A bed, and catalyst A bed is for being catalyzed
The gaseous products of pyrolytic reaction are cracked, third solids distribution device and the 4th solids distribution device are respectively used to tiling catalyst A bed
With catalyst B bed, the 4th gas distributor is used to that the gaseous products after reaction to be made to flow to condensing unit.
A further improvement of the present invention lies in that cooling device includes spiral condensing unit, circulating condensing liquid delivery pump, coke
Oily collection device, gas collector and product detection device；Spiral condensing unit, and spiral shell are provided with below lower section furnace
Rotating condensing unit entrance is connected with lower section outlet of still, and spiral condensing unit outlet is divided into two-way, all the way through gaseous product
Storage tank is connected with phase chromatograph-mass spectrometer, is provided with secondary liquid condensed product storage tank, and two below gaseous product storage tank
Secondary liquid condensed product storage tank is connected with gaseous product storage tank, and another way is through tar liquid product reservoir and phase combined gas chromatography mass spectrometry
Instrument is connected；Spiral condensing unit is also connected with circulating condensing liquid delivery pump.
A kind of directional catalyzing cracking technology, the reaction atmosphere in the reaction tube of upper section furnace tile by first gas distributor
The activation of reaction gas is carried out to catalyst bed, activation temperature is：600 DEG C~800 DEG C, reaction pressure is 0.1MPa~1MPa,
Reaction atmosphere under the action of catalyst, generates free radicals, and the free radical that free radical is generated with the raw material pyrolysis in raw material bed connects
Touching, obtained gaseous products tile by third gas distributor to catalyst A bed, and catalyst A bed is to pyrolytic reaction
Gaseous products carry out catalytic pyrolysis, and the product after catalytic pyrolysis enters catalyst B bed and carries out shape selective catalysis, after shape selective catalysis
Product enters condensing unit and is condensed, obtained tar liquid；Wherein, raw material is coal or biomass.
A further improvement of the present invention lies in that reaction atmosphere CH4、CH4And CO2Gaseous mixture, CH4With mixing for vapor
Close gas, CH4And O2Gaseous mixture, dissociated methanol gas, the mixture or dissociated methanol gas of dissociated methanol gas and oxygen and water vapour
Mixture；Wherein, CH4And CO2Gaseous mixture in, CH4And CO2Volume ratio be (1~2)：1；CH4With the gaseous mixture of vapor
In, by volume percentage, CH4It is 10%~20%, vapor is 80%~90%；CH4And O2Gaseous mixture in, by volume
Percentages, CH4For 80%~90%, O2It is 10%~20%；In the mixture of methanol and oxygen, the substance of methanol and oxygen
Amount ratio be (2~5)：1；In the mixture of methanol and water vapour, the ratio of the amount of the substance of methanol and vapor be (1~
1.5)：1.
A further improvement of the present invention lies in that the temperature of catalytic pyrolysis be 600 DEG C~800 DEG C, pressure be 0.1MPa~
1MPa；The mass ratio of raw material and the catalyst on catalyst A bed 19 is：(0.5~4)：1.
A further improvement of the present invention lies in that the temperature of shape selective catalysis be 400 DEG C~600 DEG C, pressure be 0.1MPa~
1MPa；The mass ratio of raw material and the catalyst on catalyst B bed 21 is：(0.5~2)：1.
Compared with prior art, the invention has the advantages that：
The present invention reacts the upper section furnace of tar yield and for heat by setting feeder, for improving pyrolysis of coal
Solution tar carries out catalysis and selects the lower section furnace of type, between reaction gas needed for can reasonably regulating and controlling reaction, between reaction solution or
Charge proportion between reaction gas and reaction solution, so that feeding manner is not influenced by sample introduction sample form, input mode is flexible,
Operating condition is mild, and equipment investment is smaller.Compared to the N of same condition2Or the tar yield under inert atmosphere, which can
The significant yield for improving the raw materials pyrolytic tar products such as coal, biomass, and greatly improve oil quality.
Further, due in the reaction tube in upper section furnace, from top to bottom equipped with gas distributor, catalyst bed, the
One solids distribution device, raw material bed, the second solids distribution device and second gas distributor, in the reaction tube in lower section furnace, from
Third gas distributor, catalyst A bed, third solids distribution device, catalyst B bed, the 4th solids distribution are housed up to lower
Device and the 4th gas distributor, so the distribution of the raw materials pyrolytic tar products such as regulation coal, biomass can be effectively directed.
Original sample coal passes through the process unit and method, and the light aromatics relative amount such as BTXN (benzene,toluene,xylene, naphthalene) is big in product
Width increases；Biomass passes through the process unit and method, and the relative amounts increment such as PCX (phenol, cresols, xylenol) is aobvious in product
Write, it is seen that the present apparatus can the target product to these high added values be effectively enriched with.
The raw materials such as coal, biomass are pyrolyzed to improve tar yield process and orient corresponding product by the present invention to be distributed
Journey is integrated into a set of technique, simplifies integrated artistic process, environmentally friendly, is reduced Energy Consumption Cost, is improved technique
Production efficiency, and it is easy to mass production scale, it is suitable for industrial application.Pass through the pyrolytic tars such as orientation regulation coal, biomass
The distribution of product improves the temperature, pressure and orientation goal of regulation and control tar product distribution of products collection efficiency area (fixed bed upper section furnace)
The segmentation Reasonable Regulation And Control of the temperature in area's (fixed bed lower section furnace), pressure so that integrated artistic flexible operation, have it is preferable controllable
Property.
Detailed description of the invention
Fig. 1 is single unit system structural schematic diagram of the invention.
Fig. 2 is the structural front view of upper section furnace, lower section furnace.
Fig. 3 is the structure right view of upper section furnace, lower section furnace.
Fig. 4 is spiral condensing unit structural schematic diagram.
Fig. 5 is the total ion chromatogram (N of the pyrolysis of coal gaseous state tar product of embodiment 12For reaction gas).
Fig. 6 is the total ion chromatogram of the pyrolysis of coal gaseous state tar product of embodiment 2.
Fig. 7 is the total ion chromatogram of the pyrolysis of coal gaseous state tar product of embodiment 3.
Fig. 8 is that the corn stover of embodiment 4 is pyrolyzed the total ion chromatogram of gaseous state tar product.
Fig. 9 is that the corn stover of embodiment 5 is pyrolyzed the total ion chromatogram of gaseous state tar product.
Figure 10 is that the corn stover of embodiment 6 is pyrolyzed the total ion chromatogram of gaseous state tar product.
Description of symbols, 1. first carrier gas bottles；2. the second carrier gas bottle；3. third carrier gas bottle；4. the first carrier gas flux control
Valve processed；5. the second carrier gas flux control valve；6. third carrier gas flux control valve；7. mixed gas tank；8. the total carrier gas flux control of system
Device processed；9. upper section furnace；10. lower section furnace；11. reaction tube fixed disassembly device；12. first gas distributor；13. catalyst bed
Layer；14. the first solids distribution device；15. raw material bed；16. the second solids distribution device；17. second gas distributor；18. third
Gas distributor；19. catalyst A bed；20. third solids distribution device；21. catalyst B bed；22. the 4th solids distribution device；
23. the 4th gas distributor；24. spiral condensing unit；25. circulating condensing liquid delivery pump；26. tar liquid product reservoir；
27. incubator；28. gaseous product storage tank；29. secondary liquid condensed product storage tank；30. gas chromatography-mass spectrometry；31. the
One carrier gas flux controller；32. the second carrier gas flux controller；33. third carrier gas flux controller；34. temperature in the middle part of upper section furnace
Spend controller；35. upper section furnace upper temp controller；36. upper section furnace temperature of lower controller；37. lower section furnace middle portion temperature control
Device processed；38. lower section furnace upper temp controller；39. lower section furnace temperature of lower controller；40. heating tape temperature controller；41.
Incubator temperature controller；42. controller power source master switch；43. upper section furnace and lower section furnace battery main switch；44. incubator adds
Tropical battery main switch；45. flow controller battery main switch；46. backup temperature controller；47. two sections furnace door handle
Hand；48. spiral condenser pipe；49. plunger pump；50. gaseous products channel；51. condensate outlet；52. condensate liquid import.
Specific embodiment
Invention is further described in detailed description of the present invention embodiment with reference to the accompanying drawing, these embodiments are only
It is the exemplary explanation present invention, and is not considered as limiting the invention.
Referring to Fig. 1, a kind of directional catalyzing cracker of the invention includes feeder, for improving pyrolysis of coal reaction coke
The upper section furnace 9 of oil yield carries out the lower section furnace 10, condensing unit and temperature and pressure controller that type is selected in catalysis to pyrolytic tar
Device.Wherein, feeder includes the first carrier gas bottle 1, the second carrier gas bottle 2, third carrier gas bottle 3, the first carrier gas flux control valve
4, the second carrier gas flux control valve 5, third carrier gas flux control valve 6, the mixing for different proportion reaction gas to be uniformly mixed
The total carrier gas flux controller 8 of the system of gas tank 7 and the total flow for regulating and controlling reaction gas；Gas is housed inside mixed gas tank 7
Distributor；Outlet the first carrier gas flux control valve 4 of first carrier gas bottle 1 is connected with 7 entrance of mixed gas tank, the second carrier gas bottle 2
Outlet the second carrier gas flux control valve 5 be connected with 7 entrance of mixed gas tank, the outlet of third carrier gas bottle 3 is through third carrier gas stream
Control valve 6 is connected with 7 entrance of mixed gas tank, and the outlet of mixed gas tank 7 enters through the total carrier gas flux controller 8 of system with upper section furnace 9
Mouth is connected, and upper section furnace 9 is located at 10 top of lower section furnace；Feeder, upper section furnace 9 and lower section furnace 10 are controlled with temperature and pressure
Device device is connected.Cooling device is arranged below lower section furnace 10.
Referring to figs. 2 and 3, be divided into upper, middle and lower inside upper section furnace 9 and lower section furnace 10, top, middle part and
The difference of the bed and catalyst that are arranged in lower part, can control the different reaction temperature in upper, middle and lower accordingly.
Temperature and pressure control device includes the first carrier gas flux controller 31, the second carrier gas flux controller 32, the
Three carrier gas flux controllers 33, upper section furnace middle portion temperature controller 34, upper section furnace upper temp controller 35, upper section furnace lower part temperature
Spend controller 36, lower section furnace middle portion temperature controller 37, lower section furnace upper temp controller 38, lower section furnace temperature of lower controller
39, heating tape temperature controller 40, incubator temperature controller 41, controller power source master switch 42, upper section furnace and lower section furnace electricity
Source master switch 43, incubator, heating tape battery main switch 44, flow controller battery main switch 45 and backup temperature controller
46.First carrier gas flux controller 31 is connected with the first carrier gas flux control valve 4, and the second carrier gas flux controller 32 and second carries
Flow control valves 5 are connected, and third carrier gas flux controller 33 is connected with third carrier gas flux control valve 6.
Gas can be CH in first carrier gas bottle 1, the second carrier gas bottle 2 and third carrier gas bottle 34、CO2、CO、O2Etc. high-purity
Gas, reaction process can be individually with CH4For reaction gas, or use CH4It forms with other gases and uniformly mixes in certain proportion
Gas, as reaction gas needed for reaction.The feeder can flexibly regulate and control to be mixed between various reaction gas or reaction gas
Ratio, to improve W-response efficiency.
Referring to figure 1, figure 2 and figure 3, upper section furnace 9 and 10 shape of lower section furnace are cylindrical body of the same size, and on two sections
Section furnace 9 and about 10 lower section furnace are coaxial, are in same plumb line, and center vertical is provided with reaction in upper section furnace 9 and lower section furnace 10
It manages, is provided with two sections furnace door handle 47 on upper section furnace 9 and lower section furnace 10, fire door can pass through two sections furnace door
Handle 47 is the handle in respective furnace body center, opens 0 ° to 180 ° around plumb line, is located at upper section furnace 9 and lower section furnace 10 for dismounting
Furnace stay body center reaction tube, reaction tube tube body in upper section furnace 9 and lower section furnace 10 by reaction tube fixed disassembly device 11
It is fixed on furnace body center, raw material bed 15 and catalyst bed 13 etc. needed for reaction tube is provided with reaction.The furnace of upper section furnace 9
The external position of upper, middle and lower three, is separately connected upper section furnace middle portion temperature control of the signal wire into temperature and pressure control device
Device 34 processed, upper section furnace upper temp controller 35, upper section furnace temperature of lower controller 36, are respectively used on real-time monitoring upper section furnace
Portion, middle part, temperature of lower parameter.The outer position of upper, middle and lower three of the furnace body of lower section furnace 10, is separately connected signal wire to lower section furnace
Middle portion temperature controller 37, lower section furnace upper temp controller 38, lower section furnace temperature of lower controller 39, are respectively used to adjust in real time
Control lower section furnace top, middle part, temperature of lower parameter.
In reaction tube in upper section furnace 9, from top to bottom equipped with gas distributor 12, catalyst bed 13, the first solid point
Cloth device 14, raw material bed 15, the second solids distribution device 16 and second gas distributor 17.Wherein, gas distributor 12 can make
Reaction gas is uniformly distributed in catalyst bed 13, and catalyst bed 13 is used for activating reaction gas, 14 He of the first solids distribution device
Second solids distribution device 16, which is respectively used to tiling catalyst bed 13 and raw material bed 15, second gas distributor 17, can make to be pyrolyzed
Gaseous products uniform flow after reaction carries out next step correlated response into the reaction tube of lower section furnace 10.
Upper section furnace 9 is provided with reaction above the reaction tube inlet in upper section furnace 9 for improving raw material pyrolytic tar yield
Conductance tracheae, reaction gas gas-guide tube are connected with plunger pump 49, and reaction gas is for air guide tube needed for the offer reaction into reacting furnace
Reaction gas, plunger pump 49 react required reaction solution, reaction solution CH for providing3OH or naphthane etc., when reaction solution is CH3OH
When, under suitable process conditions, CH3OH is directly pyrolyzed, CH3OH is catalyzed weight by activation of catalyst under oxidant effect
Whole, CH3OH and excessive water vapor reaction, these reaction process can provide a large amount of hydroperoxyl radical, with pyrolysis of coal generate from
It is combined by base fragment, and then improves the yield of pyrolysis of coal tar product.
In reaction tube in lower section furnace 10, third gas distributor 18, catalyst A bed 19, third are housed from top to bottom
Solids distribution device 20, catalyst B bed 21, the 4th solids distribution device 22 and the 4th gas distributor 23.Wherein, third gas
Distributor 18 can make the gaseous products after pyrolytic reaction uniformly be distributed in catalyst A bed 19, and catalyst A bed 19 is for urging
Change the gaseous products of cracking pyrolytic reaction, third solids distribution device 20 and the 4th solids distribution device 22 are respectively used to tiling catalyst
A bed 19 and catalyst B bed 21, the 4th gas distributor 23 can make the gaseous products after reaction, and uniformly flow direction is spiral cold
Solidifying device 24, is condensed.
Referring to fig. 4, condensing unit includes spiral condensing unit 24, circulating condensing liquid delivery pump 25, tar collector
26, attemperator 27, gas collector 28, product detection device 30；Spiral condensing unit is provided with below lower section furnace 10
24, and spiral 24 entrance of condensing unit is connected with the outlet of lower section furnace 10, is gaseous products in spiral condensing unit 24
Channel 50, the spiral outlet of condensing unit 24 is divided into two-way, all the way through gaseous product storage tank 28 and phase chromatograph-mass spectrometer 30
It is connected, gaseous product storage tank 28 is arranged in incubator 27, and secondary liquid condensed product is provided with below gaseous product storage tank 28
Storage tank 29, and secondary liquid condensed product storage tank 29 is connected with gaseous product storage tank 28, secondary liquid condensed product storage tank 29
It is arranged outside incubator 27, another way is connected through tar liquid product reservoir 26 with phase chromatograph-mass spectrometer 30.In addition, spiral shell
Rotating condensing unit 24 is also connected with circulating condensing liquid delivery pump 25；Condensate outlet 51 is provided on spiral condensing unit 24
With condensate liquid import 52.
Referring to Fig. 1 and Fig. 4, the condensate liquid in spiral condensing unit 24 recycle by circulating condensing liquid delivery pump 25 defeated
It send, condenser pipe in spiral condensing unit 24, helically formula rises shape, spiral cold around the transfer pipeline of gaseous products
Solidifying pipe both enhances condensation effect, in turn simplifies device preparation, reduces costs, embody preferable economy.
Through the condensed liquid tar of spiral condensing unit 24, it is collected into tar liquid product reservoir 26, not
Condensation or uncondensable gaseous products enter gaseous product storage tank 28, and gaseous product storage tank 28 is connected to downwards two not good liquors
State condensed product storage tank 29, for collecting the tar product of time condensation.The outside of gaseous product storage tank 28 is equipped with incubator 27,
Injector temperature for providing gas chromatography-mass spectrometry 30 regulates and controls.
Reaction gas in the present invention is directly with CH4For reaction gas, or the CH mixed with certain volume ratio4And CO2Gaseous mixture
For reaction gas, or with CH4It is reaction gas with excessive vapor, or with CH4With small amounts agent O2It is specific as follows for reaction gas：
Specifically, the reaction gas in the present invention can be directly with CH4For reaction gas, it is passed through the activation of catalyst bed of upper section bed
Layer 13, under the effect of the catalyst further activation, the CH after activation4Hydroperoxyl radical, the Methylene free radicals of reaction gas generation
With methyl free radicals etc. with CH4The air-flow of reaction gas, by the raw materials such as coal, biomass be pyrolyzed gaseous state tar bed, with
The free radical fragment that raw material pyrolysis generates is contacted, and the steady rate and efficiency of free radical is improved, to improve coal, biology
The raw materials pyrolytic tar yield such as matter.
Reaction gas in the present invention can be with (1~2)：The CH of 1 volume ratio mixing4And CO2Gaseous mixture be reaction gas
Atmosphere, so that CH4And CO2Catalytic reforming occurs and generates hydrogen-rich free radical component, the freedom generated with raw materials pyrolysis such as coal, biomass
Base fragment is contacted, and stablizes the free radical fragment that pyrolysis of coal generates in time, and then improve the raw materials pyrolytic tars such as coal, biomass
Yield.
Reaction gas in the present invention is with CH4It is reaction atmosphere, methane and vapor reaction obtained one with excessive vapor
Carbonoxide and hydrogen, carbon monoxide and vapor, which further react, obtains carbon dioxide and hydrogen, produces during these reactions
The free radical intermediate of raw a large amount of hydrogen-rich, these free bodies are pyrolyzed in conjunction with the free radical fragment generated with raw materials such as coal, biomass,
Improve the raw materials pyrolytic tar yields such as coal, biomass.Wherein, CH4Volume percentage, CH are pressed with the gaseous mixture of excessive vapor4
It is 10%~20%, vapor is 80%~90%.
Reaction gas in the present invention is with CH4With small amounts agent O2For reaction atmosphere, portion of methane can also be given birth to by catalysis oxidation
At hydrogen-rich component, the free radical fragment that the pyrolysis of the raw materials such as coal, biomass generates further is stabilized, corresponding tar is improved and produces
Rate.Wherein, CH4With small amounts agent O2Gaseous mixture press volume percentage, CH4It is 80%~90%, oxidant O2It is 10%
~20%.
The present invention can be using dissociated methanol gas as reaction atmosphere, can also be with dissociated methanol gas and oxygen collectively as reacting
Atmosphere, can also with dissociated methanol gas (methanol is liquid, is entered in upper section furnace by plunger pump 49, is pyrolyzed as gas, further with
Corresponding reaction gas mixing, is reacted as reaction atmosphere with raw material) and water vapour collectively as reaction atmosphere, specifically such as
Under：
Directly using methanol as reaction solution, pre- thermalization processing is carried out by upper section furnace, reaction temperature is heated to, by catalyst
After bed 13 activates, generate free radical fragment that a large amount of hydroperoxyl radical is timely generated with the raw materials pyrolysis such as coal, biomass into
Row contact and combination, can effectively improve the raw materials pyrolytic tar yield such as coal, biomass.
The reaction solution methanol can carry out partial oxidation reaction with oxygen, carry out catalysis weight by catalyst bed 13
Whole reaction forms hydrogen, and the hydroperoxyl radical in reaction process can be generated free radicals with raw materials pyrolysis such as coal, biomass and be tied
It closes, and the reaction is exothermic reaction, can provide heat for pyrolytic reaction, reduces the cost of process flow, while effectively
Improve the yield of raw material pyrolytic tar product.
Ratio between the reaction solution methanol and oxygen is：Enter the substance of the methanol and oxygen in upper section furnace 9
Amount ratio be (2~5)：1.
The reaction solution methanol can be reacted with water vapour, carry out catalytic reforming reaction by catalyst bed 13
Form hydrogen, form a large amount of hydrogen free bodies in reforming process, the classes of compounds fragment that can be formed with raw material thermal decomposition product into
Row combines, and improves pyrolytic tar products collection efficiency.
Ratio is between the reaction solution methanol and water vapour：The ratio of the amount of the substance of methanol and vapor be (1~
1.5)：1.
Substantially process flow of the invention is：With CH4Or CH4It forms with other gases and uniformly mixes in certain proportion
For gas is as reaction atmosphere, by CH4Or CH4Homogeneous mixture is formed in certain proportion with other gases, as reaction institute
The reaction gas needed, is adjusted to suitable flow and enters upper section furnace 9, uniformly tiles by first gas distributor 12 to catalyst
Bed 13 carries out the activation of reaction gas, and activation temperature (i.e. upper section reaction in furnace pipe upper temp) is：600 DEG C~800 DEG C, reaction
Pressure is 0.1MPa~1MPa.CH4In catalyst, (catalyst includes：Carried metal, alkali metal, transition metal catalyst in
Any one, catalyst carrier include molecular sieve, oxide, semicoke etc. any one) under effect, generate methyl or methylene
Equal free radicals, these free radicals are contacted with the free radical of coal or the raw materials pyrolysis generation such as biomass in raw material bed 15, can be with
The steady rate and efficiency for improving free radical, to improve the raw materials pyrolytic tar yield such as coal, biomass.Either by reaction solution
CH3OH pyrolysis, CH3OH and oxidizer catalytic reformation, CH3OH is reacted with vapor, which can equally provide a large amount of hydrogen certainly
By base, the free radical fragment generated with raw materials pyrolysis such as coal, biomass is combined, and then improves raw material pyrolytic tar product
Yield.Obtained gaseous products uniformly tile by third gas distributor 18 to catalyst A bed 19, catalyst A bed
The gaseous products of 19 pairs of pyrolytic reactions carry out catalytic pyrolysis, and the product after catalytic pyrolysis is carried out into catalyst B bed 21 into one
Shape selective catalysis is walked to orient regulation product, and then obtains ideal target product, the product after shape selective catalysis enters condensing unit
It is condensed, obtained tar liquid is collected in tar liquid product reservoir 26, and gaseous products then enter gaseous product storage tank
28, the tar liquid and gaseous products collected are sent into gas chromatography-mass spectrometry 30 and carry out on-line real-time measuremen analysis,
Product detection result, which timely feedbacks, gives temperature and pressure control device, and then adjusts the related process ginseng of each process section in real time
Number, realizes the optimization of technological parameter.Wherein, when raw material is coal, target product is benzene,toluene,xylene and naphthalene；Raw material is raw
When substance, target product is phenol, cresols, xylenol.
Catalyst packet for the mixture that priming reaction liquid or priming reaction liquid and reaction gas are mixed in a certain proportion
It includes：Cu/CeO2、CuO/CeO2、Cu/ZnO/ZrO2、Cu/ZnO/Al2O3Equal Cu series catalysts；Ni/CeO2、Ni/CeO2-ZrO2Deng
Ni series catalysts；And Pd/ZnO, Pd/La2O3、Pd/SiO2、Pd/ZrO2Equal noble metals series catalysts.
The mixture that reaction solution or reaction solution and reaction gas are mixed in a certain proportion, carries out by catalyst bed 13
Priming reaction, priming reaction temperature (upper section bed reaction tubes upper temp) are：200 DEG C~500 DEG C, reaction pressure is：
0.01MPa~0.1MPa.
The raw materials such as coal, biomass pyrolysis temperature (upper section bed reaction tubes temperature of lower) is：300 DEG C~800 DEG C, reaction pressure
Power is 0.1MPa~1MPa.
The raw material (coal or biomass) and the catalyst quality ratio of activating reaction gas (reaction solution) are：(0.5~2)：1.
Include to the process that the pyrolytic tar product of raw material carries out catalytic pyrolysis and orients regulation：Raw material pyrolytic tar
Product catalyst cracks segment process method and raw material pyrolytic tar product orientation regulation segment process method, specific as follows：
Raw material pyrolytic tar product catalyst cracks segment process method：
The invention lower section furnace 10 selects type for carrying out catalysis to raw material pyrolytic tar, to orient regulation product point
Cloth in the reaction tube in lower section furnace, is sequentially arranged with third gas distributor 18, catalyst A bed 19, solids distribution from top to bottom
Device 20, catalyst B bed 21, solids distribution device 22, the 4th gas distributor 23, catalyst A bed 19 are used for pyrolytic tar
Catalytic pyrolysis, catalyst B bed 21 is for being oriented regulation to catalytic pyrolysis product.
The gaseous state tar product that yield is improved through upper section furnace, as reaction gas flow enters lower section bed, by catalyst A bed
Macromolecular substances in gaseous state tar product are further cracked into compared with small-molecule substance by 19 progress catalytic pyrolysis, promote coal hot
Solution heavy tar is converted into tar light oil and gas, to realize the optimization of tar quality.
The catalytic pyrolysis section, gaseous state catalytic cracking of tar temperature are：600 DEG C~800 DEG C, reaction pressure 0.1MPa
~1MPa.
The catalyst of the catalyst A bed 19 includes：Predominantly carbon-supported catalysts or aluminium oxide catalyst, with half
Coke, active carbon, activated carbon fibre, carbon nanotube, graphene or aluminium oxide etc. are catalyst carrier, in these supported on carriers
The different types of metal ion such as Co, Ni, Cu, Zn, Fe, Mg, Ce, Zr, Ga of different proportion.
The mass ratio of the raw material and the catalyst of catalyst A bed 19 is：(0.5~4)：1.
Raw material pyrolytic tar product orientation regulates and controls segment process method：
Gaseous state tar product passes through catalyst A bed 19, after carrying out catalytic pyrolysis, as reaction gas flow enters catalyst B
Bed 21, the catalyst positioned at catalyst B bed 21 carry out shape selective catalysis to gaseous state tar product, and then orient regulation tar and produce
The distribution of object.
The catalyst of the catalyst B bed 21 mainly includes：Molecular sieve catalyst or carried molecular sieve catalysis
Agent.Molecular sieve catalyst includes：ZSM-5, ZSM-11, USY, HY and beta-molecular sieve etc..The metal ion of load mainly includes：
Mo and Ni etc..
The carried molecular sieve catalyst of the catalyst B bed 21, can individually load certain mass score Mo or
Ni metal ion, or Mo the and Ni metal ion of certain mass score is loaded simultaneously.
The orientation regulates and controls section, and gaseous state catalytic cracking of tar temperature is：400 DEG C~600 DEG C, reaction pressure 0.1MPa
~1MPa.
The orientation of the raw material and B bed 21 regulates and controls catalyst quality ratio：(0.5~2)：1.
The invention upper section furnace 9 and lower section furnace 10, up and down coaxially, the reaction tube of two sections furnace are located among furnace body,
Same diameter under upper, and communicate up and down, centre is separated by with gas distribution grid and sieve plate.The outside of two-stage furnace is connected with temperature controller respectively
And pressure controller, it is respectively used to temperature and pressure, the lower section reaction in furnace of the upper and lower part of control upper section reaction in furnace pipe
The temperature and pressure of the upper and lower part of pipe.
The lower section of lower section furnace 10 connects condensing unit 24, and condensing unit is used to condense the gaseous products after shape selective catalysis,
It is closed condensation tank body 24 outside condensing unit, inside is spiral condensation fluid catheter, and the condensation fluid catheter is imported and exported, with
External circulating condensing liquid delivery pump 25 is connected.
Condensing unit further connects tar collector 26 and gas collector 28, is respectively used to collect condensable coke
Oily and uncondensable gaseous product, and tar and gas collector 28 then connection product detection device 30, for tar and
The on-line checking of the constituent of gaseous product and analysis.
Product detection device 30 of the invention is gas chromatography-mass spectrometry, gas chromatography-mass spectrometry and the device
In temperature and pressure control device 31~46 be connected, for by product detection result timely feedback give temperature and pressure control
Device 31~46, and then the related process parameters of each process section are adjusted in real time, realize the optimization of technological parameter.
The following are the embodiments under different technology conditions.
Embodiment 1
Using northern Shensi chemical plant low-order coal as raw material, Industrial Analysis and elemental analysis are shown in Table 1.Experiment coal 5g, instead
Should gas be N2, catalyst activation temperature is 600 DEG C, and the catalyst for activating reaction gas is HY (also referred to as HY molecular sieve catalytic
Agent), HY dosage 2g；The temperature of pyrolysis of coal is 800 DEG C, and reaction pressure is：0.1MPa；Catalytic cracking catalyst is Al2O3, Al2O3
Dosage 2g, catalytic pyrolysis section temperature are 600 DEG C；It is Mo/Ni/HZSM-5, Mo/Ni/ for orienting regulation tar product catalyst
HZSM-5 dosage is 2g, and orientation regulation section temperature is 500 DEG C, and reaction pressure is：0.1MPa.Pyrolysis of coal tar yield is
5.63%.The component of all kinds of products of coal is distributed referring to table 2, as shown in Table 2, in the catalytic pyrolysis product of the coal after orientation regulation
Total relative amount of BTXN is 8.84%.Fig. 5 is the total ion chromatogram (N of pyrolysis of coal gaseous state tar product2For reaction
Gas), as shown in Figure 5, after orientation regulation, the GC/MS peak type of target product is larger and relatively independent, i.e., target product is had
The separation and enrichment of effect.
The Industrial Analysis and elemental analysis of 1 low-order coal of table
* minusing
The component of all kinds of products of 2 coal of table is distributed (N2For reaction gas)
Embodiment 2
Using northern Shensi chemical plant low-order coal as raw material, Industrial Analysis and elemental analysis are shown in Table 1.Experiment coal 5g, instead
Should gas be CH4, catalyst activation temperature is 600 DEG C, and the catalyst for activating reaction gas is HY, HY dosage 2g；Pyrolysis of coal
Temperature is 800 DEG C, and reaction pressure is：0.1MPa；Catalytic cracking catalyst is Al2O3, Al2O3Dosage 2g, catalytic pyrolysis section temperature
It is 600 DEG C；It is Mo/Ni/HZSM-5 for orienting regulation tar product catalyst, Mo/Ni/HZSM-5 dosage is 2g, and orientation is adjusted
Controlling section temperature is 500 DEG C, and reaction pressure is：0.1MPa.Pyrolysis of coal tar yield is 8.81%.The component of all kinds of products of coal point
Cloth is referring to table 3, and as shown in Table 3, total relative amount of BTXN is in the catalytic pyrolysis product of the coal after orientation regulation
32.94%.Fig. 6 is the total ion chromatogram of pyrolysis of coal gaseous state tar product, it will be appreciated from fig. 6 that after orientation regulation, target product
GC/MS peak type it is larger and relatively independent, i.e., target product is efficiently separated and is enriched with.
The component of all kinds of products of 3 coal of table is distributed (CH4For reaction gas)
Embodiment 3
Using northern Shensi chemical plant low-order coal as raw material, Industrial Analysis and elemental analysis are shown in Table 1.Experiment coal 5g, instead
Answering liquid is CH3OH, catalyst activation temperature are 600 DEG C, and the catalyst for activating reaction gas is HY, HY dosage 2g；Pyrolysis of coal
Temperature be 800 DEG C, reaction pressure is：0.1MPa；Catalytic cracking catalyst is Al2O3, Al2O3Dosage 2g catalytic pyrolysis Duan Wen
Degree is 600 DEG C；It is Mo/Ni/HZSM-5 for orienting regulation tar product catalyst, Mo/Ni/HZSM-5 dosage is 2g, orientation
Regulating and controlling section temperature is 500 DEG C, and reaction pressure is：0.1MPa.Pyrolysis of coal tar yield is 9.93%.The component of all kinds of products of coal
Distribution is referring to table 4, and as shown in Table 4, total relative amount of BTXN is in the catalytic pyrolysis product of the coal after orientation regulation
19.01%.Fig. 7 is the total ion chromatogram of pyrolysis of coal gaseous state tar product, as shown in Figure 7, after orientation regulation, target product
GC/MS peak type it is larger and relatively independent, i.e., target product is efficiently separated and is enriched with.
The component of all kinds of products of 4 coal of table is distributed (reaction solution CH3OH)
Embodiment 4
Using corn stover as raw material, Industrial Analysis and elemental analysis are shown in Table 5.Experiment corn stover 4g, reaction gas
For N2, catalyst activation temperature is 600 DEG C, and the catalyst for activating reaction gas is HY, HY dosage 1g；Corn stover pyrolysis
Temperature is 800 DEG C, and reaction pressure is：0.1MPa；Catalytic cracking catalyst is Al2O3, Al2O3Dosage 1g, catalytic pyrolysis section temperature
It is 600 DEG C；It is Mo/Ni/HZSM-5 for orienting regulation tar product catalyst, Mo/Ni/HZSM-5 dosage is 1g, and orientation is adjusted
Controlling section temperature is 500 DEG C, and reaction pressure is：0.1MPa.The pyrolytic tar yield of corn stover is 4.35%.Corn stover it is each
The component of class product is distributed referring to table 6, and as shown in Table 6, PCX is total in the catalytic pyrolysis product of the corn stover after orientation regulation
Relative amount is 14.04%.Fig. 8 is the total ion chromatogram that corn stover is pyrolyzed gaseous state tar product, as shown in Figure 8, fixed
To after regulation, the GC/MS peak type of target product is larger and relatively independent, i.e., target product is efficiently separated and is enriched with.
The Industrial Analysis and elemental analysis of 5 corn stover of table
* minusing
The component of all kinds of products of 6 corn stover of table is distributed (N2For reaction gas)
Embodiment 5
Using corn stover as raw material, Industrial Analysis and elemental analysis are shown in Table 5.Experiment corn stover 4g, reaction gas
For CH4, catalyst activation temperature is 600 DEG C, and the catalyst for activating reaction gas is HY, HY dosage 1g；Corn stover pyrolysis
Temperature be 800 DEG C, reaction pressure is：0.1MPa；Catalytic cracking catalyst is Al2O3, Al2O3Dosage 1g, catalytic pyrolysis Duan Wen
Degree is 600 DEG C；Catalyst for orienting regulation tar product is Mo/Ni/HZSM-5, and Mo/Ni/HZSM-5 dosage is 1g, fixed
It is 500 DEG C to regulation section temperature, reaction pressure is：0.1MPa.The pyrolytic tar yield of corn stover is 8.29%.Corn stover
All kinds of products component be distributed referring to table 7, as shown in Table 7, orientation regulation after corn stover catalytic pyrolysis product in PCX
Total relative amount is 31.01%.Fig. 9 is the total ion chromatogram that corn stover is pyrolyzed gaseous state tar product, can by Fig. 9
Know, orientation regulation after, the GC/MS peak type of target product is larger and relatively independent, i.e., target product obtained efficiently separating and
Enrichment.
The component of all kinds of products of 7 corn stover of table is distributed (CH4For reaction gas)
Embodiment 6
Using corn stover as raw material, Industrial Analysis and elemental analysis are shown in Table 5.Experiment corn stover 4g, reaction solution
For CH3OH, catalyst activation temperature are 600 DEG C, and the catalyst for activating reaction gas is HY, HY dosage 1g；Corn stover heat
The temperature of solution is 800 DEG C, and reaction pressure is：0.1MPa；Catalytic cracking catalyst is Al2O3, Al2O3Dosage 1g, catalytic pyrolysis section
Temperature is 600 DEG C；It is Mo/Ni/HZSM-5 for orienting regulation tar product catalyst, Mo/Ni/HZSM-5 dosage is 1g, fixed
It is 500 DEG C to regulation section temperature, reaction pressure is：0.1MPa.The pyrolytic tar yield of corn stover is 9.92%.Corn stover
All kinds of products component be distributed referring to table 8, as shown in Table 8, orientation regulation after corn stover catalytic pyrolysis product in PCX
Total relative amount is 29.42%.Figure 10 is the total ion chromatogram that corn stover is pyrolyzed gaseous state tar product, can by Figure 10
Know, orientation regulation after, the GC/MS peak type of target product is larger and relatively independent, i.e., target product obtained efficiently separating and
Enrichment.
The component of all kinds of products of 8 corn stover of table is distributed (reaction solution CH3OH)
Claims (10)
1. a kind of directional catalyzing cracker, which is characterized in that including feeder, for improving pyrolysis of coal reaction tar yield
Upper section furnace (9), for pyrolytic tar carry out catalysis select type lower section furnace (10), cooling device and temperature and pressure control
Device device；Upper section furnace (9) and lower section furnace (10) are cylindrical body, and two sections of upper section furnaces (9) and lower section furnace (10) are coaxial up and down,
Upper section furnace (9) and lower section furnace (10) interior center vertical are provided with reaction tube；Feeder is connected with upper section furnace (9), feeder,
Upper section furnace (9) and lower section furnace (10) are connected with temperature and pressure control device；Cooling device is arranged in lower section furnace (10)
Lower section.
2. a kind of directional catalyzing cracker according to claim 1, which is characterized in that feeder includes the first carrier gas
Bottle (1), the second carrier gas bottle (2), third carrier gas bottle (3), the first carrier gas flux control valve (4), the second carrier gas flux control valve
(5), the total carrier gas stream of the system of third carrier gas flux control valve (6), mixed gas tank (7) and the total flow for regulating and controlling reaction gas
Amount controller (8)；Outlet the first carrier gas flux control valve (4) of first carrier gas bottle (1) is connected with mixed gas tank (7) entrance,
Outlet the second carrier gas flux control valve (5) of second carrier gas bottle (2) is connected with mixed gas tank (7) entrance, third carrier gas bottle (3)
Outlet be connected through third carrier gas flux control valve (6) with mixed gas tank (7) entrance, mixed gas tank (7) outlet always carried through system
Air-flow amount controller (8) is connected with upper section furnace (9) entrance.
3. a kind of directional catalyzing cracker according to claim 2, which is characterized in that temperature and pressure control device
Including the first carrier gas flux controller (31), the second carrier gas flux controller (32), third carrier gas flux controller (33), upper section
Furnace middle portion temperature controller (34), upper section furnace upper temp controller (35), upper section furnace temperature of lower controller (36), lower section furnace
Middle portion temperature controller (37), lower section furnace upper temp controller (38) and lower section furnace temperature of lower controller (39)；First
Carrier gas flux controller (31) is connected with the first carrier gas flux control valve (4), and the second carrier gas flux controller (32) is carried with second
Flow control valves (5) are connected, and third carrier gas flux controller (33) is connected with third carrier gas flux control valve (6)；Upper section furnace
(9) the outer position of upper, middle and lower three of furnace body, is separately connected signal wire in the upper section furnace into temperature and pressure control device
Portion's temperature controller (34), upper section furnace upper temp controller (35), upper section furnace temperature of lower controller (36), lower section furnace (10)
The outer position of upper, middle and lower three of furnace body, be separately connected signal wire to lower section furnace middle portion temperature controller (37), lower section furnace top
Temperature controller (38), lower section furnace temperature of lower controller (39).
4. a kind of directional catalyzing cracker according to claim 1, which is characterized in that the reaction tube in upper section furnace (9)
It is interior, from top to bottom equipped with gas distributor (12), catalyst bed (13), the first solids distribution device (14), raw material bed (15),
Second solids distribution device (16) and second gas distributor (17)；Wherein, gas distributor (12) is for keeping reaction gas uniform
Be distributed in catalyst bed, catalyst bed (13) is used for activating reaction gas, the first solids distribution device (14) and the second solid
Distributor (16) is respectively used to tiling catalyst bed (13) and raw material bed (15), and second gas distributor (17) is for making heat
Gaseous product stream after solution reaction is into the reaction tube of lower section furnace (10).
5. a kind of directional catalyzing cracker according to claim 4, which is characterized in that the reaction tube in lower section furnace (10)
It is interior, third gas distributor (18), catalyst A bed (19), third solids distribution device (20), catalyst B are housed from top to bottom
Bed (21), the 4th solids distribution device (22) and the 4th gas distributor (23)；Wherein, third gas distributor (18) is used for
For gaseous product distribution after making pyrolytic reaction in catalyst A bed (19), catalyst A bed (19) is anti-for catalytic pyrolysis pyrolysis
The gaseous products answered, third solids distribution device (20) and the 4th solids distribution device (22) are respectively used to tiling catalyst A bed
(19) and catalyst B bed (21), the 4th gas distributor (23) are used to that the gaseous products after reaction to be made to flow to condensing unit.
6. a kind of directional catalyzing cracker according to claim 1, which is characterized in that cooling device includes spiral cold
Solidifying device (24), circulating condensing liquid delivery pump (25), tar collector (26), gas collector (28) and product detection
Device (30)；Be provided with spiral condensing unit (24) below lower section furnace (10), and spiral condensing unit (24) entrance with
Lower section furnace (10) outlet is connected, and the outlet of spiral condensing unit (24) is divided into two-way, all the way through gaseous product storage tank (28) with
Phase chromatograph-mass spectrometer (30) is connected, and is provided with secondary liquid condensed product storage tank (29) below gaseous product storage tank (28),
And secondary liquid condensed product storage tank (29) is connected with gaseous product storage tank (28), and another way is through tar liquid product reservoir
(26) it is connected with phase chromatograph-mass spectrometer (30)；Spiral condensing unit (24) is also connected with circulating condensing liquid delivery pump
(25)。
7. a kind of directional catalyzing cracking technology based on claim 5 described device, which is characterized in that the reaction of upper section furnace (9)
Reaction atmosphere in pipe, which tiles by first gas distributor (12) to catalyst bed (13), carries out the activation of reaction gas, activation
Temperature is：600 DEG C~800 DEG C, reaction pressure is 0.1MPa~1MPa, and reaction atmosphere under the action of catalyst, generates free radicals,
Free radical is contacted with the free radical that the raw material pyrolysis in raw material bed (15) generates, and obtained gaseous products are by third gas point
To catalyst A bed (19), catalyst A bed (19) carries out catalysis to the gaseous products of pyrolytic reaction and splits for cloth device (18) tiling
It solves, the product after catalytic pyrolysis enters catalyst B bed (21) and carries out shape selective catalysis, and the product after shape selective catalysis enters condensation dress
It sets and is condensed, obtained tar liquid；Wherein, raw material is coal or biomass.
8. directional catalyzing cracking technology according to claim 7, which is characterized in that reaction atmosphere CH4、CH4And CO2's
Gaseous mixture, CH4Gaseous mixture, CH with vapor4And O2Gaseous mixture, dissociated methanol gas, dissociated methanol gas and oxygen mixture
Or the mixture of dissociated methanol gas and water vapour；Wherein, CH4And CO2Gaseous mixture in, CH4And CO2Volume ratio be (1~2)：
1；CH4In the gaseous mixture of vapor, by volume percentage, CH4It is 10%~20%, vapor is 80%~90%；CH4
And O2Gaseous mixture in, by volume percentage, CH4For 80%~90%, O2It is 10%~20%；The mixing of methanol and oxygen
In object, the ratio of the amount of the substance of methanol and oxygen is (2~5)：1；In the mixture of methanol and water vapour, methanol and vapor
The ratio of the amount of substance is (1~1.5)：1.
9. directional catalyzing cracking technology according to claim 7, which is characterized in that the temperature of catalytic pyrolysis be 600 DEG C~
800 DEG C, pressure is 0.1MPa~1MPa；The mass ratio of raw material and the catalyst on catalyst A bed 19 is：(0.5~4)：1.
10. directional catalyzing cracking technology according to claim 7, which is characterized in that the temperature of shape selective catalysis be 400 DEG C~
600 DEG C, pressure is 0.1MPa~1MPa；The mass ratio of raw material and the catalyst on catalyst B bed 21 is：(0.5~2)：1.
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