CN102260516B - Method for preparing oil by thermally cracking biomass - Google Patents
Method for preparing oil by thermally cracking biomass Download PDFInfo
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- CN102260516B CN102260516B CN 201110177922 CN201110177922A CN102260516B CN 102260516 B CN102260516 B CN 102260516B CN 201110177922 CN201110177922 CN 201110177922 CN 201110177922 A CN201110177922 A CN 201110177922A CN 102260516 B CN102260516 B CN 102260516B
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- 238000005336 cracking Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000002028 Biomass Substances 0.000 title claims abstract description 26
- 239000003921 oil Substances 0.000 claims abstract description 66
- 238000000926 separation method Methods 0.000 claims abstract description 51
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 239000002994 raw material Substances 0.000 claims abstract description 40
- 230000008569 process Effects 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000003502 gasoline Substances 0.000 claims abstract description 8
- 239000002283 diesel fuel Substances 0.000 claims abstract description 7
- 230000007017 scission Effects 0.000 claims description 44
- 238000003776 cleavage reaction Methods 0.000 claims description 42
- 239000007789 gas Substances 0.000 claims description 41
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 13
- 239000003546 flue gas Substances 0.000 claims description 13
- 238000000197 pyrolysis Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000005235 decoking Methods 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 241000195493 Cryptophyta Species 0.000 claims description 4
- 241000196324 Embryophyta Species 0.000 claims description 4
- 235000007164 Oryza sativa Nutrition 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 239000010903 husk Substances 0.000 claims description 4
- 239000013502 plastic waste Substances 0.000 claims description 4
- 235000009566 rice Nutrition 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- 239000010902 straw Substances 0.000 claims description 3
- 238000005382 thermal cycling Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000005194 fractionation Methods 0.000 claims description 2
- 238000002513 implantation Methods 0.000 claims description 2
- 230000008676 import Effects 0.000 claims description 2
- 239000000779 smoke Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 238000004939 coking Methods 0.000 abstract description 8
- 239000010724 circulating oil Substances 0.000 abstract description 7
- 230000003111 delayed effect Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 238000005086 pumping Methods 0.000 abstract 2
- 230000005855 radiation Effects 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 238000004227 thermal cracking Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010504 bond cleavage reaction Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 206010020843 Hyperthermia Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 230000036031 hyperthermia Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a technology for preparing oil by thermally cracking biomass, and particularly provides a method for preparing the oil by thermally cracking biomass and the like which are taken as raw materials. The method relies on a technology similar to delayed coking. The method mainly comprises the following steps of: pumping circulating oil out from the bottom of a fractionating column, pumping into a radiation chamber furnace tube of a heating furnace by a hot oil pump, quickly heating and raising the temperature to 450 to 550 DEG C, feeding into the upper part of a thermal cracking tower, spraying onto raw material stack layers by a distributor, allowing raw material cracking oil gas and the circulating oil to flow to the bottom of the cracking tower from up to down along the raw material stack layers so as to form the temperature gradient from up to down; and allowing the raw material cracking oil gas and the circulating oil to enter a vapor-liquid separation tank, allowing the raw material cracking oil gas obtained after separation to enter the fractionating column, performing mass transfer on the raw material cracking oil and the mixed liquid of cracking liquid and the circulating oil, and fractionating to obtain gas, crude gasoline, diesel oil, wax oil and circulating oil. The method has the main characteristics of energy conservation along with reasonable process, and low cost.
Description
Technical field
The present invention relates to thermally splitting and produce the oil gas technical field, be specifically related to the thermo-cracking method of making oil such as a kind of biomass.
Background technology
At present, not outer following several with the method for biomass liquefaction: destructive distillation, high-temperature flue gas heating, fluidized-bed, nitrated, fermentation.Above method exists following shortcoming to be: the destructive distillation heating efficiency is low, and thermograde is large, is difficult to heavy industrialization; High-temperature flue gas heating products oxygen level is high, and a large amount of low heating value gass are good utilisation not; Fluidized-bed is to the selection that processed raw material, and the raw material that molecule is processed in inconvenience uses; Nitrated use strong acid, facility investment is large, long flow path; Fermenting speed is slow, and the product separation energy consumption is high, difficulty is large.
Can find out many rural areas are arranged because reclaim stalk every year and there is no benefit from relevant report in the past, the big area of setting fire is everywhere burned, and not only causes environmental pollution, and causes disadvantageous effect for highway communication and air transportation.That is to say up to the present, also there is no a kind of better method that passes through the thermo-cracking liquefaction take biomass, plastic waste, waste rubber and garbage organism as raw material.
Summary of the invention
Purpose of the present invention is exactly the defective that exists for prior art, provides a kind of flow process reasonable, with low cost, energy-conservation biomass through pyrolysis method of making oil.
Its technical scheme comprises: take one or more of biomass, plastic waste, waste rubber or garbage organism as raw material, through the method for making oil of thermo-cracking and fractionation process process, wherein biomass comprise the one or more combination of straw, rice husk, branch, leaf, weeds or algae.
(1), after the populated raw material of cleavage column, from the flue gas of 180 ~ 290 ℃ of cleavage column bottom implantation temperatures, to the raw material dehydration, flue gas and take off rear steam by the high some blow-off valve emptying of cleavage column top; After cleavage column upper, middle and lower temperature is all over 180 ℃, close hot smoke valve, utilize 180 ~ 300 ℃ of superheated vapours of temperature to displace flue gas and emptying, after displacement, close superheated vapour and high some blow-off valve.
(2), after external turning oil accesses vapor-liquid separation tank, separation column bottom, process furnace successively by pipe connecting and pump, produce two loops by control valve, one the tunnel gets back to vapor-liquid separation tank, form initial cycles oil and inject and soft circulation circuit, in this circulation, the heating and temperature control of process furnace is at 300 ~ 350 ℃.
(3), after completing turning oil injection and thermal cycling, closed control valve is to the loop of vapor-liquid separation tank, another access cleavage column top, loop, be sprayed onto on the stockpile layer through sparger, the vapour that sets up separately by cleavage column bottom and bottom again, the liquid outlet imports vapor-liquid separation tank, after temperature that raw material cracking oil gas and turning oil enter vapor-liquid separation tank is higher than 375 ℃, open the Fractionator Bottom pump, use from the turning oil fast cooling of Fractionator Bottom through interchanger, the temperature that enters the vapor-liquid separation tank medium is controlled at 350 ~ 370 ℃ (preventing coking), vapour after vapor-liquid separation tank separates, the pipeline of liquid by separately enters the separation column bottom, the separation column bottom is connected with external turning oil pipeline with interchanger by pump, form turning oil thermo-cracking circulation loop.
(4), be provided with a plurality of discharge ports according to the separate substance different boiling on separation column, enter oil gas in separation column by its boiling point height successively the discharge port by separately by heat exchange, the cooling product tank field of entering.
Such scheme also comprises: rise in 450 ~ 550 ℃ in the temperature that turning oil is gone out process furnace, occupy the cleavage column upper space from cleavage column top injection dry gas.
The position of the oil after vapor-liquid separation tank separates, vapour access separation column is by upper and lower layout.
The discharge port that arranges on separation column comprises turning oil, wax oil, diesel oil, gasoline and gas from bottom to top, and wherein the gasoline of cracking generation and gas are sent into downstream absorption-stabilizing deyice after the gas compressor compression, separate to get dry gas, liquefied gas and stable gasoline.
Described cleavage column has two at least, and vapor-liquid separation tank is corresponding one by one with the cleavage column formation, and described control valve is four-way valve, and the cleavage column decoking utilizes water vapor stripping, cooling burnt layer to carry out after below 70 ℃.
Described biomass comprise straw, rice husk, branch, leaf, weeds, algae etc.
The present invention compared with prior art, its advantage applies is in the following aspects:
The high temperature circulation oil Direct Uniform of 1, coming from process furnace is sprayed onto on the pile of biomass layer, and thermo-efficiency is high, and rate of heat transfer is high, and co-altitude raw material layer temperature is even, and different heights is the formation temperature gradient from top to bottom, there is no localized hyperthermia's phenomenon.
2, two above cleavage column blocked operations just as delayed coking unit, can be processed raw material on a large scale, realize the industrialization continuous operation.
3, utilize high temperature circulation oil to provide heat to biomass through pyrolysis, there is no air in cleavage column, also do not need indifferent gas heating fluidisation, the product oxygen level is naturally lower, and dry gas is also high heat value gas.
4, high temperature circulation oil Direct Uniform is sprayed onto on the pile of biomass layer, is easy to control thermo-cracking speed and reaction depth, has also just realized the control of yield of cracked product and quality.
5, can use this technological transformation to have delayed coking unit, less investment, instant effect.
6, cracking stock wide material sources, not only can process biomass, as stalk, rice husk, branch, leaf, weeds, algae etc., all right treatment of waste plastics, waste rubber and garbage organism, both can individual curing same class raw material, also can process simultaneously different types of raw material.
7, cracking stock does not need to be ground into small-particle, only needs simple cutting, and the raw materials pretreatment expense is lower.
8, high temperature circulation oil Direct Uniform is sprayed onto on the pile of biomass layer, and biomass can arrive the thermo-cracking temperature fast, and the fractionating technology of product utilization maturation is cut, and energy consumption is low, easily processes.
Description of drawings
Fig. 1 is schematic flow sheet of the present invention.
in Fig. 1, marking explanation is as follows: 1 is process furnace, 2, 3 (can arrange N cleavage column according to process scale for cleavage column, only be illustrated with 2 cleavage columns in accompanying drawing 1), 4, 5 is vapor-liquid separation tank, 6 is separation column, 7 is the overhead product vapor-liquid separation tank, 8 is the diesel oil stripping tower, 9 are cracking liquid and turning oil mixing liquid pump, 10 is the raw gasline pump, 11 is the tower top recycle pump, 12 is the stage casing recycle pump, 13 is diesel oil pump, 14 is the wax oil pump, 15 is circulating oil pump, 16 is the Fractionator Bottom pump, 17 ~ 21 is water cooler, 22 ~ 26 is interchanger, 27 is four-way valve, 28 is product gas, 29 is raw gasline, 30 is diesel oil, 31 is wax oil, 32 is turning oil, 33 is coke, 34, 35 is raw material, 36 is dry gas, 37 is the emptying of high point, 38 is hot flue gas, 39 is superheated vapour, 40 is stripping oil gas and safety valve emptying oil gas before decoking.
Embodiment
Below in conjunction with accompanying drawing 1, be described further with 20,000 ton/years of biomass through pyrolysis method of making oil.
As can be seen from Figure 1, at first, turning oil 32 enters vapor-liquid separation tank 4 or 5 by water cooler 21 and interchanger 25,26 pairs of lines outside installing, after setting up liquid level, start cracking liquid and turning oil mixing liquid pump 9, after liquid level is set up in separation column 6 bottoms, start circulating oil pump 15, turning oil is squeezed into process furnace 1 radiator tube be warming up to 300 ~ 350 ℃, enter vapor-liquid separation tank 4 or 5 by four-way valve 27, set up the turning oil thermal cycling.(front preparation step 1 goes into operation)
simultaneously, raw material 34 through simple cutting, the 35(raw material comprises biomass, plastic waste, waste rubber and garbage organism) enter cleavage column 2 or 3 by the feeder (not shown), after being added to proper height, open hot flue gas 38(130 ~ 250 ℃) enter the cleavage column bottom, in the process that rises, dewater to raw material, flue gas and take off rear steam and put emptying 37 by height, when cleavage column upper, middle and lower homo(io)thermism after 180 ~ 200 ℃, close hot flue gas 38, unlatching superheated vapour 39(180 ~ 300 ℃) displacement flue gas and emptying, after displacement, close superheated vapour 39 and the emptying 37 of high point.(front preparation step 2 goes into operation)
then, turning oil is changed into cleavage column 2 or 3 tops by four-way valve 27, be sprayed onto on the stockpile layer through sparger, at this moment, the temperature that turning oil is gone out process furnace 1 rises to 450 ~ 550 ℃ (the raw material scission reaction needs high temperature), (heat scission reaction is thermo-negative reaction to need simultaneously supply response heat, these heats need to bring raw material from the turning oil of process furnace fully), raw material cracking oil gas and turning oil flow to cleavage column bottom along raw material layer from top to bottom, lower floor's raw material has obtained the heat that upper strata raw material cracking oil gas and turning oil carry, form thermograde (550 ~ 320 ℃) from top to bottom, the outlet that is positioned at centrum bottom is mainly used in cracking liquid and the turning oil mixed solution goes out tower, another or a plurality of outlet that is positioned on centrum limit wall or vertical tower wall are mainly used in raw material cracking oil gas and go out tower, cracking liquid enters vapor-liquid separation tank 4 or 5 together with converging to after turning oil goes out cleavage column.
After temperature that raw material cracking oil gas and turning oil enter vapor-liquid separation tank 4 or 5 is higher than 375 ℃, open Fractionator Bottom pump 16, use from the turning oil fast cooling of Fractionator Bottom through interchanger 26, the temperature that enters vapor-liquid separation tank 4 or 5 media is controlled at 350 ~ 370 ℃ (preventing coking), raw material cracking oil gas after separation enters separation column 6, cracking liquid and turning oil mixed solution are squeezed into separation column 6 through pump 9, and it enters the tower height degree and enters on the tower mouth at raw material cracking oil gas.
Rise in 450 ~ 550 ℃ in the temperature that turning oil is gone out process furnace 1, open in right amount dry gas 36 from cleavage column top injection, occupy the cleavage column upper space with dry gas, can reduce raw material cracking oil gas in the cleavage column residence time, to reduce the secondary cracking ratio.
In separation column, different according to boiling point, tell successively turning oil 32, wax oil 31, diesel oil 30, tower top distillates raw gasline 29 and gas 28, the gas 28 that cracking produces is delivered to downstream absorption-steady component (not shown) together with raw gasline 29 after gas compressor compression (not shown), separate to get dry gas, liquefied gas and stable gasoline, this patent separation column and downstream absorption-steady component and delayed coking unit in like manner just repeat no more.
When cleavage column thermograde from top to bottom progressively is changed to 550 ~ 530 ℃ from 550 ~ 320 ℃, and the amount that raw material cracking oil gas enters separation column 6 sharply reduces, at this moment, can determine that the raw material thermo-cracking finishes in this cleavage column, simultaneously turning oil is changed into another cleavage column top by four-way valve 27.
Cleavage column originally utilizes water vapor stripping, cooling burnt layer (with steam and water) to begin decoking after below 70 ℃, and before decoking, stripping oil gas and safety valve emptying oil gas 40 enter downstream cooling system (not shown).The program of cleavage column decoking and Coking Tower for Delayed Coking Unit in like manner just repeat no more here.
In the cleavage column decoking, remove vapor-liquid separation tank 4 or 5 deposit coke.
Claims (5)
1. biomass through pyrolysis method of making oil, take one or more of biomass, plastic waste, waste rubber or garbage organism as raw material, method of making oil through thermo-cracking and fractionation process process, wherein biomass comprise the one or more combination of straw, rice husk, branch, leaf, weeds or algae, it is characterized in that:
(1), after the populated raw material of cleavage column, from the flue gas of 180 ~ 290 ℃ of cleavage column bottom implantation temperatures, to the raw material dehydration, flue gas and take off rear steam by the high some blow-off valve emptying of cleavage column top; After cleavage column upper, middle and lower temperature is all over 180 ℃, close hot smoke valve, utilize 180 ~ 300 ℃ of superheated vapours of temperature to displace flue gas and emptying, after displacement, close superheated vapour and high some blow-off valve;
(2), after external turning oil accesses vapor-liquid separation tank, separation column bottom, process furnace successively by pipe connecting and pump, produce two loops by control valve, one the tunnel gets back to vapor-liquid separation tank, form initial cycles oil and inject and soft circulation circuit, in this circulation, the heating and temperature control of process furnace is at 300 ~ 350 ℃;
(3), after completing turning oil injection and thermal cycling, closed control valve is to the loop of vapor-liquid separation tank, another access cleavage column top, loop, be sprayed onto on the stockpile layer through sparger, the temperature that this moment, turning oil went out process furnace rises to 450-550 ℃, the vapour that sets up separately by cleavage column bottom and bottom again, the liquid outlet imports vapor-liquid separation tank, after temperature that raw material cracking oil gas and turning oil enter vapor-liquid separation tank is higher than 375 ℃, open the Fractionator Bottom pump, use from the turning oil fast cooling of Fractionator Bottom through interchanger, the temperature that enters the vapor-liquid separation tank medium is controlled at 350 ~ 370 ℃, vapour after vapor-liquid separation tank separates, the pipeline of liquid by separately enters the separation column bottom, the separation column bottom is connected with external turning oil pipeline with interchanger by pump, form turning oil thermo-cracking circulation loop,
(4), be provided with a plurality of discharge ports according to the separate substance different boiling on separation column, enter oil gas in separation column by its boiling point height successively the discharge port by separately by heat exchange, the cooling product tank field of entering.
2. biomass through pyrolysis method of making oil according to claim 1, is characterized in that: rise in 450 ~ 550 ℃ in the temperature that turning oil is gone out process furnace, occupy the cleavage column upper space from cleavage column top injection dry gas.
3. biomass through pyrolysis method of making oil according to claim 1 and 2 is characterized in that: the position of the oil after vapor-liquid separation tank separates, vapour access separation column is by upper and lower layout.
4. biomass through pyrolysis method of making oil according to claim 3, it is characterized in that: the discharge port that arranges on separation column comprises turning oil, wax oil, diesel oil, gasoline and gas from bottom to top, wherein the gasoline of cracking generation and gas are sent into downstream absorption-stabilizing deyice after the gas compressor compression, separate to get dry gas, liquefied gas and stable gasoline.
5. biomass through pyrolysis method of making oil according to claim 4, it is characterized in that: described cleavage column has two at least, vapor-liquid separation tank consists of corresponding one by one with cleavage column, described control valve is four-way valve, and the cleavage column decoking utilizes water vapor stripping, cooling burnt layer to carry out after below 70 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110177922 CN102260516B (en) | 2011-06-29 | 2011-06-29 | Method for preparing oil by thermally cracking biomass |
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| CN 201110177922 CN102260516B (en) | 2011-06-29 | 2011-06-29 | Method for preparing oil by thermally cracking biomass |
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| CN102260516A CN102260516A (en) | 2011-11-30 |
| CN102260516B true CN102260516B (en) | 2013-06-19 |
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| TW201332672A (en) * | 2012-02-07 | 2013-08-16 | Zhuang Rong | Waste recycling method and device thereof |
| CN103571527B (en) * | 2013-11-15 | 2015-07-01 | 合肥工业大学 | Preparation method of high-calorific-value nonpolar bio-oil/gasoline homogeneous fuel oil |
| CN105716052B (en) * | 2014-12-02 | 2018-04-06 | 上海优华系统集成技术有限公司 | A kind of high-temperature flue gas heat integration optimizes system |
| CN108611104B (en) * | 2018-06-19 | 2024-05-24 | 天津大学 | Integrated method and equipment for separating and recovering energy of oil sand pyrolysis oil gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1891789A (en) * | 2005-07-06 | 2007-01-10 | 华东理工大学 | Delayed coking treatment method for waste biomass |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1891789A (en) * | 2005-07-06 | 2007-01-10 | 华东理工大学 | Delayed coking treatment method for waste biomass |
Non-Patent Citations (1)
| Title |
|---|
| 张振华，汪华林，陈于勤，胥培军.利用延迟焦化方法处理生物质的技术可行性分析.《可再生能源》.2007,第25卷(第5期), * |
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