CN103980921B - Industrial production method of fuel oil by thermal cracking of biomass - Google Patents
Industrial production method of fuel oil by thermal cracking of biomass Download PDFInfo
- Publication number
- CN103980921B CN103980921B CN201410233201.6A CN201410233201A CN103980921B CN 103980921 B CN103980921 B CN 103980921B CN 201410233201 A CN201410233201 A CN 201410233201A CN 103980921 B CN103980921 B CN 103980921B
- Authority
- CN
- China
- Prior art keywords
- gas
- biomass
- heater
- oil
- heat carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002028 Biomass Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000295 fuel oil Substances 0.000 title claims abstract description 29
- 238000004227 thermal cracking Methods 0.000 title claims abstract description 14
- 238000009776 industrial production Methods 0.000 title abstract 2
- 239000002994 raw material Substances 0.000 claims abstract description 38
- 239000010779 crude oil Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 238000005859 coupling reaction Methods 0.000 claims abstract description 10
- 238000005336 cracking Methods 0.000 claims abstract description 10
- 230000008878 coupling Effects 0.000 claims abstract description 8
- 238000010168 coupling process Methods 0.000 claims abstract description 8
- 238000007670 refining Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000004821 distillation Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 63
- 238000000197 pyrolysis Methods 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 32
- 239000004033 plastic Substances 0.000 claims description 23
- 229920003023 plastic Polymers 0.000 claims description 23
- 239000002699 waste material Substances 0.000 claims description 23
- 239000000567 combustion gas Substances 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 19
- 238000007789 sealing Methods 0.000 claims description 16
- 238000009833 condensation Methods 0.000 claims description 13
- 230000005494 condensation Effects 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 230000007017 scission Effects 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 230000007246 mechanism Effects 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000010504 bond cleavage reaction Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 230000003068 static effect Effects 0.000 claims description 7
- 229920000742 Cotton Polymers 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 239000010902 straw Substances 0.000 claims description 6
- 239000006004 Quartz sand Substances 0.000 claims description 5
- 239000003610 charcoal Substances 0.000 claims description 5
- 238000013461 design Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 241000209140 Triticum Species 0.000 claims description 3
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000010903 husk Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 19
- 239000002551 biofuel Substances 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 7
- 239000002023 wood Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000003912 environmental pollution Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000010815 organic waste Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002154 agricultural waste Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- 229910052756 noble gas Inorganic materials 0.000 description 2
- 150000002835 noble gases Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 208000001613 Gambling Diseases 0.000 description 1
- 208000036626 Mental retardation Diseases 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 208000011117 substance-related disease Diseases 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Processing Of Solid Wastes (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides an industrial production method of fuel oil by thermal cracking of biomass and relates to the technical field of thermal cracking of biomass and renewable resources. The method mainly comprises the following steps that raw materials are prepared; the raw materials and a thermal carrier are subjected to thermal coupling in a horizontal roller rotating cracking furnace with the internal thermal carrier, and then thermal cracking, solid-gas separation, biological crude oil distillation and catalytic refining are conducted; non-condensable gas is used as a heat resource for a thermal cracking reaction; the heat carrier is maintained in the furnace to continuously participate in the reaction; biological crude oil is subjected to esterifying distillation and catalyzing and then is condensed to obtain the biofuel products; and cracking is conducted in the horizontal roller rotating cracking furnace with the internal thermal carrier. By virtue of the process disclosed by the invention, the defects of the prior art are overcome, the catalytically refined fuel oil has the characteristics of high calorific value, good liquidity and good stability; the process is reasonable, simple in control, convenient, energy-saving, high in production efficiency, especially strong in suitability for raw materials, simple in equipment and convenient to operate.
Description
Technical field
The present invention relates to biomass cracking and Renewable resource technical field.
Background technology
Face exhaustion and environmental pollution increasingly serious today in the non-renewable resources frequency such as oil, natural gas, the energy needs
Seek the two big problems becoming the world today with environmental conservation.Compared with fossil resource, biomass are renewable, environmental pollution is little,
Do not produce CO2Discharge, is one of most common Renewable resource on the earth.With the raising of people's living standard, house refuse
In content of organics gradually rise, burial processes and can not meet the requirement of environmental protection, burns decrement treatment and can produce two English
The nuisance of class.Therefore, develop that to be suitable for the thermal cracking process equipment of difference Organic substances be the urgent of the utilization of resources and environmental conservation
Demand.
Solid organic matters thermal cracking produces in the various techniques of liquid fuel, and reactor is its core.According to biology
The feature of matter thermal cracking, rapid cleavage and rapid condensation are the maximum yield reaching liquid fuel, therefore commonly used both at home and abroad
Be fluidized-bed reactor.But, due to itself biochemical composition and construction featuress, this kind of material cracking reaction oil productivity is not high,
Gained oil quality is not good, and for example oxygen content is high, and calorific value and stability are all undesirable, and therefore limiting its industrialized popularization should
With.Biomass of Tsing-Hua University's invention and take the plastics copyrolysis newly square (patent No.：CN 102618312 A), experiment can make biology
Oily oxygen content is relatively low, and calorific value reaches more than the 90% of crude oil, expands the scope of application of bio-fuel-oil.Exploitation both at home and abroad is anti-at present
Answer device species a lot, define different techniques, each defective, mainly point following several types：
（1）Mechanical contact reactor process, the common ground of this kind of reactor be by heating response device surface directly or
Indirectly contact with biomass, transfer heat to biomass so as to high-speed heating, reach the purpose of rapid cleavage.It adopts
Heat transfer mode be conduction of heat, common are ablation pyrolysis reactor, silk screen pyrolysis reactor, rotating cone reactor etc..
But it is big to there is equipment attrition, power consumption big it is difficult to the problem amplified of industrialization.
（2）Indirect reaction device technique, the surface or the thermal source offer life that are mainly characterized by a high temperature of this kind of reactor
Heat energy needed for material pyrolysis, it mainly carries out heat conduction by heat radiation, and common thermobalance ownership is such, as reality
Test room equipment and be difficult to industrialization amplification.
（3）Mixing reactor, mixing reactor mainly carries out to biomass by thinking stream thermal current and gas-solid soon more
Speed heating, the mode playing leading heat transfer is mainly heat convection, but heat radiation and conduction of heat also be can not ignore, and common are
Fluidized-bed reactor, quick injection bed reactor, circulating fluid bed reactor etc..Wherein circulating fluidized bed device is because solving heat
Amount conversion, realizes heat self-sufficiency, is well positioned to meet the requirement to heating rate for the fast pyrogenation and is widely used.Use at present
It is conveying bed and recirculating fluidized bed series in commercial off-the-shelf.Fluidized bed reactor to crushing material require higher and it needs to
Substantial amounts of carrier gas, reclaims difficult to the incoagulability combustion gas in producing.House refuse is mainly with waste plastics and is susceptible to adhesion gambling
Match, the bad adaptability to raw material.
（4）Vacuum moving-burden bed reactor, vacuum moving-burden bed reactor is two by high-temperature molten salt heating response device puts down
Plate, material carries out thermal cracking during transmitting in the horizontal plate of two heating.This technique needs substantial amounts of hot blast as heat
The drive energy of carrier.Fluid bed is to enter pyrolysis furnace as heat carrier with material using 500 ° about noble gases to carry out coupling
Close reaction, noble gases together discharge out of the furnace with cracking gas, cause condensation recovery difficulty and incoagulable gas pure as combustion gas
Degree reduces the utilization of impact combustion gas.Fluid bed class reactor, because not having power drive, easily causes waste plastics in thermal histories
Adhesion blocks, and is not suitable for the copyrolysis of biomass and waste plastics.The production technology of now domestic several biomass through pyrolysis is only
It is limited to the biomass liquefying stage, the calorific value of biological liquid fuel is 16-18mj/kg, be 1.5 times about of biomass calorific value,
Re-refine and be extremely limited, therefore domestic at present technique does not have process for refining substantially.Biomass are in reactor thermal cracking
When undesirable gas and solid thermal carriers, therefore, decrease the subsequent volume of bio-fuel-oil collection system and cost, but need
A set of Molten salt heating system.Because this reactor needs powerful vacuum pump, price is high, energy consumption is big, amplifies difficult, therefore mesh
Front China does not have unit research.In addition, common biomass pyrolysis device also has:Fixed bed pyrolysis reactor, freedom
Fall pyrolysis reactor etc..But study in China less at present, be not detailed here.Biomass pyrolysis for liquid production technology is
Start research and development from developed country, China is that recent years is inchoate, as the agricultural of " do not strive grain with the people, do not strive ground with grain "
Garbage is general as maximum R＆D direction, biomass through pyrolysis principle, but because being different techniques, the effect of generation
Fruit difference is very big.Above-mentioned domestic and international the deficiencies in the prior art are summarized as follows：
1st, fluid bed is not enough：Operation has high demands, and the preparation of non-reactive fluidizing gas, circulation, heating and cooling energy consumption are big in a large number, rule
The big intermittent fever of mould is less efficient, harsh to the particle diameter of raw material, shape need, considerably increases the processing cost of raw material.
2nd, there is cinder wear problem in circulating fluid bed reactor, and is not easy to use of maximizing；
Rotating cone reactor is not enough：Run up part, and energy consumption is big, and operation easier is big.
3rd, vacuum moving-burden bed reactor is higher for vacuum level requirements, increased manufacturing cost and runs difficulty.
Content of the invention
The problem to be solved in the present invention is to provide a kind of industrialized preparing process of biomass through pyrolysis fuel oil, overcomes
The deficiency of prior art, rational technology, through catalytic refining post fuel oil, calorific value is higher, good fluidity, good stability；Operation letter
Just, energy-conservation, production efficiency are high, and especially strong to raw material suitability, different agriculture and forestry organic waste materials such as straw, wood flour, bark, branch etc. are all
Can use；Equipment is simple, low cost, also eliminates environmental pollution, particularly suitable large scale industry while reducing production cost
Change production and application, huge social efficiency and business efficiency can be produced.
The main technical schemes of the present invention are：A kind of biomass through pyrolysis produce the technique of fuel oil it is characterised in that wrapping
Include following steps：
A, preparation raw material：Raw material is biomass, through drying；Described biomass material is cotton stalk and branch, saw
End, wood shavings, wheat straw, Caulis et Folium Oryzae, rice husk；Or raw material is biomass and waste plastics, biomass with the Mixing ratio by weight example of waste plastics are：
7 parts of biomass, waste plastics >=2 part；
B, raw material are carried out thermal coupling in the rotary pyrolysis furnace of built-in heat carrier and carry out heat scission reaction with heat carrier：
Generate ash and oil gas；
C, the ash generating after completion of the reaction and oil gas carry out gas solid separation：Ash is discharged, and obtains biology after oil gas condensation
Crude oil and incoagulability combustion gas, biological crude oil enters pans；On-condensible gas also can condensed gas-liquid separation again, obtain biological hair
Oil；Last incoagulability combustion gas returns the thermal source of the gas nozzle being used as pyrocrack furnace heat scission reaction heater, and unnecessary is right
Outer conveying；Heat carrier stays thermal coupling and the heat scission reaction that material is newly entered in multiple participation in stove always；
D, biological crude oil distillation catalytic refining：Rectification maximum temperature is not more than 360 DEG C, and incoagulability combustion gas is as rectifying column
The heat energy of middle rectification, after rectification removes solid impurity and high boiling fraction in crude oil, indirect steam pour point depression catalytic tower, in catalysis
In tower, after the effect of catalyst, condensation obtains bio-fuel-oil product.
Improve further, described step d, in, through esterification treatment operation before distilling and being catalyzed, even if methanol and life
Material cracking produces accompaniment wood vinegar and esterification occurs, to improve fuel qualities.（This section should be removed）
Described catalyst is：The modified molecular sieve of FCC, SBA-15, MCM-41, SCPO-11 and Zn, Mn, Fe, its
One or more of；Catalytic amount is the 1%--20% of raw material weight, for the purpose of bio-fuel-oil pour point depression.
Preferably, described heat carrier is quartz sand.
Preferably, charging in the rotary pyrolysis furnace of built-in heat carrier for the described raw material is continuous feed.
Preferably, described ash discharges mode：Ash is by being expelled to charcoal from after cooling sealing flood dragon 20 cooling
Storage room；Do the thermal source of raw material stoving using the flue residue heat in pyrocrack furnace, be used as the low-temperature receiver of oil gas condensation with biological crude oil.
Preferably, the rotary pyrolysis furnace of described built-in heat carrier is the horizontal drum rotation pyrolysis furnace of built-in heat carrier,
It is characterized in that, including horizontal rotary body of heater, this horizontal rotary body of heater is placed in burner hearth, two rotating shafts of horizontal rotary body of heater with
It is dynamic sealing between burner hearth, in burner hearth, is provided with heater, heater is gas nozzle；Hearth wall is provided with furnace gas export, horizontal rotary
Two rotating shafts of body of heater are the hollow pipe with the inner space of horizontal rotary body of heater, and one of hollow pipe is derived for gaseous mixture
Pipe, mixing gas delivery line end dynamic sealing connects static delivery line；Another hollow pipe is feed pipe, at described feed pipe
It is provided with sealed feeding mechanism；Horizontal rotary body of heater is placed on carrying roller or axle bed, hollow pipe pass through mechanical driving device with
Motor is connected；Heat carrier is distributed with the circumference in horizontal rotary body of heater and turns over flight, it is one that described heat carrier turns over flight
The radial skew plate of row and axis parallel or parallel-plate.
Preferably, the structure of described sealed feeding mechanism is：Conveying pipeline gos deep in stove in feed pipe, and conveying pipeline is from entering
Expects pipe is dynamic sealing, and the rear portion of conveying pipeline is provided with hopper and pusher mouth, and the reciprocating charging ram of reciprocating feeder is from pusher mouth
Place enters pusher, and reciprocating charging ram is connected with reciprocating power mechanism；Described feed pipe leaves raw material seal section, by adjusting
The length of the Stroke Control seal section of whole reciprocating feeder, conveniently can realize continuous feed, greatly improve productivity ratio.
Preferably, described last incoagulability combustion gas is delivered to gas holder through roots blower, and the combustion gas in gas holder is through through back-fire relief
Device, does the combustion gas of the gas nozzle of heater.
Described biomass material can be used directly, cotton stalk and branch, and diameter is less than 3mm, and length does not limit；Also may be used
Use after pulverizing.
The positive effect of the present invention is：The problem to be solved in the present invention is to provide a kind of biomass through pyrolysis to produce fuel oil
Technique, overcome the deficiency of prior art, rational technology, through catalytic refining post fuel oil calorific value is higher, good fluidity, stable
Property is good；Easy and simple to handle, energy-conservation, production efficiency are high, especially strong to raw material suitability, different agriculture and forestry organic waste materials such as straw, wood flour, tree
Skin, branch etc. all can use；Equipment is simple, low cost, also eliminates environmental pollution while reducing production cost, especially suitable
Preferably large industrialized production and application, can produce huge social efficiency and business efficiency.
This technique is very strong to the suitability of raw material, to different agriculture and forestry organic waste materials such as straw, wood flour, bark, branch and former
Material particle diameter shape etc. all has good lytic effect, and variation of operating parameters is little.This equipment operation is simple, easy to control, non-
Often meet the dispersion of the agricultural wastes place of production, the practical situation such as operative employee is mostly little educational and technique drill is not enough.Mental retardation
Consumption, the advantages of production efficiency is high, can achieve and for flammable fixed gas circulating and recovering to heat pyrolysis furnace, therefore energy consumption is very low.With stream
Change bed to compare, be not required to a large amount of non-reactive fluidizing gas circulations, substantially increase production efficiency.Whole process no carrier gas use, and do not coagulate
Property combustion gas purity high, the heat energy as pyrolysis and rectification avoids the secondary pollution in production.Waste plastics is as good fortune hydrogen Organic substance
Use, decrease the investment of catalytic hydrogenation equipment and the loaded down with trivial details production technology during fuel oil refines, also effectively reduce day
The pollution to environment for the waste plastics that benefit increases.
Brief description
Fig. 1 is technological process and the schematic device of the present invention.
Fig. 2 is the structural representation of the horizontal drum rotation pyrolysis furnace of built-in heat carrier used in Fig. 1.
Fig. 3 is the A-A generalized section in Fig. 2.
In Fig. 1,1, reciprocating feeder, 5, gas nozzle, 11, rotation pyrolysis furnace, 16, dry raw material, 19, bipolar rotation
Point, 20, self cooling sealing auger, 21, crude oil cooler, 22, spray column, 23, pans, 24, rectifying column, 25, catalytic tower, 26,
Water condenser, 27, gas-liquid separator, 28, roots blower, 29, gas holder, 30 flue gases, 31, roller drier, 32, raw material, 33,
Charcoal exports, and 34, bio-fuel-oil outlet, 35, gas outlet；
In Fig. 2～Fig. 3：1st, reciprocating feeder, 2, feed pipe, 3, material envelope section, 4, carrying roller, 5, gas nozzle, 6. heat carry
Body（Quartz sand）, 7, burner hearth, 8, motor, 9, gear ring, 10, mixing gas delivery line, 11, horizontal rotary body of heater, 12, heat carrier
Turn over flight, 13, conveying pipeline, 14, dynamic sealing, 15, mixed gas outlet, 16, raw material, 17 thermocouples, 18, static delivery line.
Specific embodiment
In order that the creation characteristic that this utility model is realized is easy to understand with effect, with reference to embodiment and above-mentioned
Accompanying drawing is described further, but not as a limitation of the invention.
Process example 1：
Referring to Fig. 1, this biomass through pyrolysis produces the technique of fuel oil it is characterised in that comprising the following steps：
A, preparation raw material：Raw material is biomass, through drying；Described biomass material is cotton stalk and branch, saw
End, wood shavings, wheat straw, waste plastics, Caulis et Folium Oryzae, rice husk；
Or raw material is biomass and waste plastics, biomass with the Mixing ratio by weight example of waste plastics are：7 parts of biomass, give up and mould
>=2 parts of material（As 2,3,5,7 etc., more also can, only waste plastics also can use）；Effect all can reach requirement.
B, raw material are carried out thermal coupling in the rotary pyrolysis furnace of built-in heat carrier and carry out heat scission reaction with heat carrier：
Generate ash and oil gas；
C, the ash generating after completion of the reaction and oil gas carry out gas solid separation：Ash is discharged, and obtains biology after oil gas condensation
Crude oil and incoagulability combustion gas, biological crude oil enters pans；On-condensible gas also can condensed gas-liquid separation again, obtain biological hair
Oil；Last incoagulability combustion gas returns the thermal source of the gas nozzle being used as pyrocrack furnace heat scission reaction heater, and unnecessary is right
Outer conveying；Heat carrier stays thermal coupling and the heat scission reaction that material is newly entered in multiple participation in stove always；
D, biological crude oil distillation catalytic refining：Rectification maximum temperature is not more than 360 DEG C, and incoagulability combustion gas is as rectifying column
The heat energy of middle rectification, after rectification removes solid impurity and high boiling fraction in crude oil, indirect steam pour point depression catalytic tower, in catalysis
In tower, in the presence of catalyst, condensation obtains bio-fuel-oil product.
Described catalyst is：Modified molecular sieve of FCC, SBA-15, MCM-41, SCPO-11 and Zn, Mn, Fe etc.,
Therein one or more；Catalytic amount is the 1%--20% of raw material weight, for the purpose of bio-fuel-oil pour point depression, can be dropped with condensation point
Low more than 30 DEG C.
Described heat carrier is quartz sand.Do the thermal source of raw material stoving using the flue residue heat in pyrocrack furnace, with biology
Crude oil is used as the low-temperature receiver of oil gas condensation.
Described ash discharges mode：Ash is by being expelled to charcoal storage from after cooling sealing flood dragon 20 cooling
Room.
Described biomass material refer to agricultural wastes, forestry waste, house refuse organic waste one of solid etc. or
Several mixing, can go to match suitable raw material according to the customer requirement of fuel oil.
Different material is not significantly distinguished to thermal cracking.Described biomass material can be used directly, cotton stalk and
Branch, diameter is less than 3mm, and length does not limit.Described waste plastics refers to house refuse organic solid waste, industrial refuse garbage such as：
Polypropylene（PP）, high density polyethylene (HDPE)（HDPE）, Low Density Polyethylene（LDPE）Deng one kind and several.It is useless according to waste plastics
The not high feature of gurry purity, addition does not have strict restriction, is to eliminate the oxygen in biomass with the good fortune hydrogen in waste plastics
Come to determine, only maximize the calorific value that the oxygen removing inside bio-fuel-oil just can lift bio-fuel-oil,
Other do not describe part is prior art, and those skilled in the art all can implement（Therefore slightly）.
Referring to Fig. 2, Fig. 3, described step b, the rotary pyrolysis furnace of built-in heat carrier structure：Including horizontal rotation
Rotary furnace body 11, this horizontal rotary body of heater 11 is placed in burner hearth 7, is close between two rotating shafts of horizontal rotary body of heater 11 and burner hearth 7
Envelope, is provided with heater, burner hearth 7 wall is provided with furnace gas export, the flue gas of furnace gas export can enter dehydrator in burner hearth 7；Horizontal rotary
Two rotating shafts of body of heater 11 are the hollow pipe with the inner space of horizontal rotary body of heater 11, and one of hollow pipe is gaseous mixture
Delivery line 10, mixing gas delivery line 10 end dynamic sealing 14 connects static delivery line 17, equipped with thermoelectricity in static delivery line 17
Even 18；Static delivery line is convenient to connect follow-up equipment.Another hollow pipe is feed pipe 2；Horizontal rotary body of heater 11 is placed in carrying roller 4
Or on axle bed, a hollow pipe is connected with motor 8 by mechanical driving device；Divide on circumference in horizontal rotary body of heater 11
It is furnished with heat carrier and turn over flight 12.Described heater is gas nozzle 5.Described gas nozzle 5 is 4-6, positioned at horizontal rotation
Below the left part of rotary furnace body 11, near charging pipe end.Described heat carrier turns over the radial direction that flight 12 is a row and axis parallel
Hang plate.2 pairs of described carrying rollers 4 are respectively placed in the side-lower with 2 hollow pipes of the inner space of horizontal rotary body of heater 11.Institute
It is provided with sealed feeding mechanism 1 at the feed pipe 2 stated.The structure of described sealed feeding mechanism 1 is：Conveying pipeline 13 is from charging
Go deep in pipe 2 in stove, conveying pipeline 13 is dynamic sealing from feed pipe 2, and the rear portion of conveying pipeline 13 is provided with hopper and pusher mouth, reciprocating
The reciprocating charging ram of feeder 1 enters pusher at pusher mouth, and reciprocating charging ram is connected with reciprocating power mechanism.Described
Reciprocating power mechanism be actuator cylinder.Described feed pipe (13) leaves raw material seal section 3, by adjusting reciprocating charging
The length of the Stroke Control seal section 3 of device 1.Described mechanical driving device is equipped with driven gear ring 9 outside mixing gas delivery line
And the gear coordinating with it.
In design and manufacture process, in stove horizontal rotary body 11, design 8-10 block heat carrier turns over flight 12, and carries
Certain axial angle is it is ensured that heat carrier is stayed in stove in the impulsive force seething elimination cracking gas.Heat carrier turns over flight 12 and carries
There is radial angle it is ensured that heat carrier and ash have the distance of fall of maximum it is ensured that cracking completely ash cleaved gas band as early as possible
Go out body of heater.The material envelope section of 3-4 times of bore reserved by feed pipe 2, reaches the sealing state of continuous feed.Burner hearth 7 has multiple gas injections
Mouth 5 provides heat energy, and body of heater 11 is placed in burner hearth, and two rotary shafts keep flat and are placed on 4 support rods 4, under the driving of motor 8
Rotate counterclockwise on carrying roller, built-in quartz sand stir-fries in the presence of flight 12 in stove as heat carrier 6, feed pipe 13 from
Go deep into concentric with charging aperture in stove in feed pipe 2, equipped with dynamic sealing 14 between feed pipe 13 and feed pipe 2, feed pipe 13 leaves
Raw material seal section 3, the length of the Stroke Control seal section 4 of adjustment hydraulic feed device 1, the outlet of body of heater is mixing gas delivery line
10, equipped with driven gear ring 9, drive body of heater rotation by motor 8.During work, burner hearth 7 has multiple gas nozzles to provide heat energy,
Heat carrier is placed in rotation pyrolysis furnace, drives body of heater rotation, heating by motor, built-in heat carrier stir-fries body of heater flight
The rapid coupled reaction of biomass that is lower and continuously entering, makes biomass material be cracked into oil gas and discharges out of the furnace together with ash.Logical
Thermal cracking temperature is checked in the transmission crossing the thermocouple 6 at static delivery line 17, and adjustment gas flow controls in-furnace temperature.Heat carrier
By gravity and flight angle design stay be heated in stove and with material recently continuous coupled reaction complete operate continuously process.
It mainly has body of heater, motor, carrying roller, heating furnace to constitute.
There is advantages below：
（1）Do dehydrator thermal source using flue residue heat.
（2）Reciprocating hydraulic charging avoids conventional helical feeder and is afraid of the drawbacks of be wound around, and so that most material is not required to
Pulverize, greatly reduce materiel machining cost.
（3）, there is not the tacky material that is heated in wide adaptability（As waste plastics）Adhesion and blockage problem.
（4）Catalytic refining post fuel oil calorific value height, good fluidity, good stability.
（5）Configuration blower fan and gas holder, make production engineering produce micro-vacuum state, are that safety coefficient greatly improves.Receive completely
Collected the most high-quality combustion gas of incoagulable gas in producing, you can meet itself using outer, remaining can externally convey, clothes
Business periphery, also eliminates environmental pollution while reducing production cost.
（6）Thermal cracking adopts the rotation pyrolysis furnace of built-in heat carrier, special suitable good fortune hydrogen Organic substance（Waste plastics）With biomass
Copyrolysis produces high-quality fuel oil.
Through test, effect is fine.Bio oil oxygen content is relatively low, and calorific value can reach more than the 90% of crude oil.
Above description illustrates principle and the flow process of this production technology, in the range of without departing from the design principle, also can
There are various equivalent variations and improve deformation, these changes and improvements broadly fall into the protection domain of this patent.
Claims (3)
1. a kind of industrialized preparing process of biomass through pyrolysis fuel oil is it is characterised in that comprise the following steps：
A, preparation raw material：Raw material is biomass, through drying；Described biomass material is cotton stalk and branch, sawdust, plane
Flower, wheat straw, Caulis et Folium Oryzae, rice husk；Or raw material is biomass and waste plastics, biomass with the Mixing ratio by weight example of waste plastics are：Biological
7 parts of matter, waste plastics >=2 part；
B, raw material are carried out thermal coupling in the rotary pyrolysis furnace of built-in heat carrier and carry out heat scission reaction with heat carrier：Generate
Ash and oil gas；
C, the ash generating after completion of the reaction and oil gas carry out gas solid separation：Ash is discharged, and obtains biological crude oil after oil gas condensation
With incoagulability combustion gas, biological crude oil entrance pans；Incoagulable gas condensed gas-liquid separation again, obtains biological crude oil；Finally
Incoagulability combustion gas return the thermal source of the gas nozzle being used as pyrocrack furnace heat scission reaction heater, unnecessary external conveying；
Heat carrier stays thermal coupling and the heat scission reaction that material is newly entered in multiple participation in stove always；
D, biological crude oil distillation catalytic refining：Rectification maximum temperature is not more than 360 DEG C, and incoagulability combustion gas is as essence in rectifying column
The heat energy evaporating, after rectification removes solid impurity and high boiling fraction in crude oil, indirect steam pour point depression catalytic tower, in catalytic tower
After the effect of catalyst, condensation obtains bio-fuel-oil product；
The charging of the rotary pyrolysis furnace in built-in heat carrier for the raw material is continuous feed；
Described ash discharges mode：Ash passes through from cooling sealing flood dragon（20）It is expelled to charcoal storage room after cooling；
Do the thermal source of raw material stoving using the flue residue heat in pyrocrack furnace, be used as the low-temperature receiver of oil gas condensation with biological crude oil；
The rotary pyrolysis furnace of described built-in heat carrier is the horizontal drum rotation pyrolysis furnace of built-in heat carrier, and its feature exists
In including horizontal rotary body of heater（11）, this horizontal rotary body of heater（11）It is placed in burner hearth（7）Interior, horizontal rotary body of heater（11）Two
Individual rotating shaft and burner hearth（7）Between be dynamic sealing, burner hearth（7）Inside it is provided with heater, heater is gas nozzle（5）；Burner hearth（7）Wall sets
There are furnace gas export, horizontal rotary body of heater（11）Two rotating shafts be and horizontal rotary body of heater（11）Inner space hollow
Pipe, one of hollow pipe is mixing gas delivery line（10）, mix gas delivery line（10）End dynamic sealing（14）Connect static
Delivery line（17）；Another hollow pipe is feed pipe（2）, described feed pipe（2）Place is provided with sealed feeding mechanism（1）；Sleeping
Formula rotating furnace body（11）It is placed in carrying roller（4）Or on axle bed, a hollow pipe passes through mechanical driving device and motor（8）Phase
Even；Horizontal rotary body of heater（11）Heat carrier is distributed with interior circumference and turns over flight（12）, described heat carrier turns over flight（12）For
One row and axis parallel and the unidirectional hang plate of the uneven row of radial direction；
In stove horizontal rotary body（11）The heat carrier of interior design turns over flight（12）With radial angle it is ensured that heat carrier and ash have
It is ensured that cracking completely ash, cleaved gas takes body of heater out of to maximum distance of fall as early as possible；
Thermal cracking adopts the rotation pyrolysis furnace of built-in heat carrier, and the special good fortune hydrogen Organic substance waste plastics that is suitable for is produced with biomass copyrolysis
, there is not be heated tacky material such as waste plastics adhesion and blockage problem in high-quality fuel oil；
Described sealed feeding mechanism（1）Structure be：Conveying pipeline（13）From feed pipe（2）Inside go deep in stove, conveying pipeline
（13）From feed pipe（2）For dynamic sealing, conveying pipeline（13）Rear portion be provided with hopper and pusher mouth, reciprocating feeder（1）Past
Compound charging ram enters pusher at pusher mouth, and reciprocating charging ram is connected with reciprocating power mechanism；Described feed pipe
(13) leave raw material seal section（3）, by adjusting reciprocating feeder（1）Stroke Control seal section（3）Length so that real
Existing continuous feed, greatly improves productivity ratio；Reciprocating hydraulic feeds, and makes most material not need to pulverize, reduces material
Processing cost；Described biomass material directly uses, cotton stalk and branch, and diameter is less than 3mm, and length does not limit.
2. a kind of industrialized preparing process of biomass through pyrolysis fuel oil according to claim 1 is it is characterised in that institute
The catalyst stated is：The modified molecular sieve of FCC, SBA-15, MCM-41, SCPO-11 and Zn, Mn, Fe, therein a kind of or
Several；Catalytic amount is the 1%--20% of raw material weight, for the purpose of bio-fuel-oil pour point depression；Described heat carrier is quartz sand；Former
The charging of the rotary pyrolysis furnace in built-in heat carrier for the material is continuous feed；Described ash discharges mode：Ash passes through certainly
Cooling sealing flood dragon（20）It is expelled to charcoal storage room after cooling；Do raw material stoving using the flue residue heat in pyrocrack furnace
Thermal source, is used as the low-temperature receiver of oil gas condensation with biological crude oil.
3. a kind of industrialized preparing process of biomass through pyrolysis fuel oil according to claim 1 is it is characterised in that
Incoagulability combustion gas afterwards is through roots blower（28）It is delivered to gas holder（29）, the combustion gas in gas holder is through through spark arrester, making heater
Gas nozzle（5）Combustion gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410233201.6A CN103980921B (en) | 2014-05-29 | 2014-05-29 | Industrial production method of fuel oil by thermal cracking of biomass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410233201.6A CN103980921B (en) | 2014-05-29 | 2014-05-29 | Industrial production method of fuel oil by thermal cracking of biomass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103980921A CN103980921A (en) | 2014-08-13 |
| CN103980921B true CN103980921B (en) | 2017-02-15 |
Family
ID=51273094
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410233201.6A Active CN103980921B (en) | 2014-05-29 | 2014-05-29 | Industrial production method of fuel oil by thermal cracking of biomass |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103980921B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316727B (en) * | 2016-08-30 | 2018-10-02 | 许畅 | A kind of porous particulated ammonium oil explosive and preparation method thereof |
| CN106433733A (en) * | 2016-09-30 | 2017-02-22 | 华南理工大学 | Device and method for producing liquid fuel through straw-waste plastic pyrolysis |
| CN107142122A (en) * | 2017-07-05 | 2017-09-08 | 李宏江 | Underground HTHP biomass fuel process units |
| SG11202000176XA (en) | 2018-04-28 | 2020-02-27 | Beijing Sanju Environmental Protection & New Materials Co Ltd | Conversion process for organic material |
| CN109536196B (en) * | 2018-04-28 | 2020-11-06 | 北京三聚环保新材料股份有限公司 | Biomass two-stage conversion process |
| CN109852426B (en) * | 2019-02-01 | 2024-10-18 | 中国科学技术大学 | A kind of biomass rotary continuous pressurized feeding device and method |
| CN113137475A (en) * | 2020-01-19 | 2021-07-20 | 招远市汇潮新能源科技有限公司 | Rotary sealing device and cracking equipment |
| CN111499235A (en) * | 2020-04-27 | 2020-08-07 | 罗敏涛 | Portland cement processing technology |
| CN111676039A (en) * | 2020-07-23 | 2020-09-18 | 东北农业大学 | A biomass pyrolysis carbonization system |
| CN111996067B (en) * | 2020-09-21 | 2024-05-17 | 山东天力能源股份有限公司 | Closed-cycle roasting oil extraction system and process |
| CN112480946B (en) * | 2020-11-20 | 2021-12-31 | 邵阳学院 | Vacuum degree adjustable device for co-pyrolysis of waste plastics and biomass and use method |
| CN114196424A (en) * | 2021-12-13 | 2022-03-18 | 中野环保科技(重庆)股份有限公司 | Recycling treatment method of hazardous waste in pharmaceutical industry |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2397116Y (en) * | 1999-07-08 | 2000-09-20 | 邢力 | Equipment for preparing hydrocarbon oil by using waste tyre and organic waste material |
| CN1710025A (en) * | 2005-06-08 | 2005-12-21 | 王述洋 | Three-conical double water innercooling biomass flash-cracked biofuel-making reactor |
| CN101220285A (en) * | 2007-12-19 | 2008-07-16 | 山东理工大学 | Double drum solid heat carrier biomass pyrolysis reactor |
| CN101560405A (en) * | 2009-05-25 | 2009-10-21 | 顾赛 | Method for preparing liquid fuels by self-heating self-circulating thermal cracking of biomass and device thereof |
| CN201605246U (en) * | 2010-01-13 | 2010-10-13 | 苏忠 | Organism and biomass dry distillation, heating and cracking device |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602953B (en) * | 2009-07-22 | 2013-02-13 | 李效时 | Purification system of straw quick thermal cracking products |
| CN202152330U (en) * | 2011-08-04 | 2012-02-29 | 孔永平 | Production system by utilizing biomass raw material for making gasoline and diesel directly |
| CN102618312B (en) * | 2012-03-27 | 2014-12-24 | 清华大学 | New method for preparing fuel oil by co-pyrolysis of biomass and waste plastic |
| CN203159540U (en) * | 2013-01-16 | 2013-08-28 | 周鼎力 | Device for continuously producing fuel oil by waste plastics and/or waste rubber |
| CN103695021B (en) * | 2014-01-03 | 2015-07-08 | 北京林业大学 | A method for preparing pyrolysis oil by co-pyrolysis and liquefaction of biomass and waste tires |
-
2014
- 2014-05-29 CN CN201410233201.6A patent/CN103980921B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2397116Y (en) * | 1999-07-08 | 2000-09-20 | 邢力 | Equipment for preparing hydrocarbon oil by using waste tyre and organic waste material |
| CN1710025A (en) * | 2005-06-08 | 2005-12-21 | 王述洋 | Three-conical double water innercooling biomass flash-cracked biofuel-making reactor |
| CN101220285A (en) * | 2007-12-19 | 2008-07-16 | 山东理工大学 | Double drum solid heat carrier biomass pyrolysis reactor |
| CN101560405A (en) * | 2009-05-25 | 2009-10-21 | 顾赛 | Method for preparing liquid fuels by self-heating self-circulating thermal cracking of biomass and device thereof |
| CN201605246U (en) * | 2010-01-13 | 2010-10-13 | 苏忠 | Organism and biomass dry distillation, heating and cracking device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103980921A (en) | 2014-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103980921B (en) | Industrial production method of fuel oil by thermal cracking of biomass | |
| CN201567310U (en) | A biomass spiral pyrolysis device | |
| CN106281397B (en) | Field biomass through pyrolysis oil refining apparatus based on solar energy heating and from heat supply | |
| CN103964903B (en) | Anaerobic and aerobic fermentation coupling device for organic garbage treatment | |
| CN107892931A (en) | The apparatus and method that portable pyrolysis prepares charcoal | |
| CN102786990B (en) | Biomass and coal fluidized bed co-gasification method | |
| CN107364860A (en) | A kind of method that efficient cryogenic carbonization prepares straw biological charcoal | |
| CN102071042A (en) | Intelligentized continuous quick microwave cracking device for biomass and waste of biomass | |
| CN102329631A (en) | Revolving-scraper type biomass pyrolysis reactor | |
| CN109721442A (en) | A kind of system and method preparing oil, gas and charcoal base manure using agricultural-forestry biomass Poly-generation | |
| CN104312602B (en) | Continuous carbonization furnace for waste wood chips | |
| CN108342211A (en) | Novel biomass pyrolysis comprehensive utilization process and system | |
| CN104974812A (en) | Method for producing clean coal (carbon) spheres by using municipal sludge and agricultural wastes | |
| CN104861997A (en) | Biomass pyrolysis reaction system and pyrolysis method | |
| CN100357396C (en) | Method and device for thermolysis preparing liquid fuel from steam explosion stalk fermented residue | |
| CN203938645U (en) | A kind of horizontal drum rotation pyrolyzer of built-in thermal barrier | |
| CN107033934B (en) | Biomass rotary propulsion pyrolysis device | |
| CN104861994A (en) | Cooling device of biomass carbonization furnace | |
| CN206828444U (en) | Continuous rotary carbide furnace | |
| CN104017597B (en) | A kind of catalytic pyrolysis of biomass system and method | |
| CN204824732U (en) | Industry fuel oil apparatus for producing is prepared in pyrolysis of agriculture and forestry abandonment living beings | |
| CN203728762U (en) | Movable rotary barrel type continuous carbonization furnace | |
| CN206173269U (en) | Open -air living beings thermal cracking oil refining equipment based on solar energy collection and from heat supply | |
| CN206318709U (en) | Utilize system of the vinegar lees for activated carbon | |
| CN206279102U (en) | The system that a kind of utilization straw prepares biomass carbon base urea fertilizer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180528 Address after: 054700 Hou Jia village, Guding Township, Weixian County, Xingtai, Hebei province (Xinggang Zhai Kou East Road, 100 m road south) Patentee after: Hebei eight degree Biological Technology Co., Ltd. Address before: 057200 Ma Lan North Village, Quzhou village, Quzhou County, Handan, Hebei Patentee before: Cao Wenxiang |
|
| TR01 | Transfer of patent right |