CN100386408C - Delayed coking treatment method for waste biomass - Google Patents
Delayed coking treatment method for waste biomass Download PDFInfo
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- CN100386408C CN100386408C CNB2005100275414A CN200510027541A CN100386408C CN 100386408 C CN100386408 C CN 100386408C CN B2005100275414 A CNB2005100275414 A CN B2005100275414A CN 200510027541 A CN200510027541 A CN 200510027541A CN 100386408 C CN100386408 C CN 100386408C
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Abstract
The invention offers delayed coking processing method used to process discarded biomass in large scale and effectively produce biomass energy sources. It belongs to discarded biomass processing field. And the method includes the follows steps: smashing the material to 0.1-2mm granularity; mixing it with oil with 0.05-15% mass ratio; heating to 190-300 centigrade degree; further heating to 420-510 centigrade degree; processing delayed coking; fractionating the oil gas product to gain fractionated product.
Description
Technical field
The present invention relates to the process field of abandoned biomass, more particularly, the present invention relates to a kind of method of handling abandoned biomass with delay coking process.
Background technology
Biomass are meant the various organism that utilize photosynthesis to obtain on the earth in a broad sense, comprise phyteral, animal matter, agriculture and forestry organic waste material, organic domestic waste etc., are a kind of stable renewable resourcess.The biomass resource of China is abundant, but 5,000,000,000 tons of whole nation production in every year biomass, and wherein the output of the culled wood produced of agroforestry, agricultural crop straw the like waste is very big.Along with improving constantly of Chinese Urbanization level, the output of city organic domestic waste is also increasing in the biomass resource.According to statistics, the output of Shanghai City domestic waste in 2000 reaches 6,410,000 tons, expects 2010 and will reach 8,630,000 tons.In the domestic refuse major part be that the kitchen is surplus, abandoned biomass such as pericarp and waste paper.People wish to realize minimizing, the harmless treatment of these abandoned biomass, effectively utilize abandoned biomass production biomass energy.
A kind of common processing mode is that abandoned biomass is carried out fast pyrolysis.This mode with the exsiccant powdered biomass in secluding air, normal pressure, high heating rate (about 10
3-10
4℃/second), carry out scission reaction under the middle temperature (about 450-500 ℃), the condition in ultrashort reaction times (about 2 seconds), generate inflammable gas, liquid fuel, liquid chemical (for example acetate, acetone etc.) and coke, its liquid yield can reach more than 60%.But the general fluidized-bed reactor that uses needs fluidisation heat-transfer medium (for example sand, quartz sand etc.) and fluidized gas to guarantee harsh processing condition in the production process of this technology, and this has just increased the complicacy of fast pyrolysis reactive system.The present domestic fast pyrolysis reactive system that does not still have suitable large-scale industrial production.
United States Patent (USP) 5,543,061 discloses the method and apparatus that a kind of abandoned biomass pyrolysis transforms, and purpose is to handle abandoned biomass innoxiously and reclaim shelf characteric source (combustion gas, fuel oil and coke).Its technical process is a two-step reaction: pulverizing after raw material is mixed with water is slurry, and first compressive reaction (pressure 4-6MPa, temperature 200-350 ℃) destroys the long molecular chain of raw material, and flash-evaporation dehydration is isolated the heavy bio oil then.Bio-crude oil is rapidly heated under normal pressure to about 500 ℃, continues reaction then, produces lightweight oil, coke powder and combustion gas.But this treatment process needs pressurization, flash distillation and constant-pressure and high-temperature reactions steps, and device fabrication cost height also is not suitable for scale operation at present.
United States Patent (USP) 4,666,585 disclose a kind of technology, send into delayed coking unit after refinery mud (most of for solids, You Heshui) and coking distillate mixed, make it have good flowability, then with at the bottom of coking raw material oil advances people's coking Tata, utilizing the waste heat of coking or crossing residual heat makes the organic constituent in the mud become coking gas-liquid product through high temperature pyrolysis, solid product is caught and is deposited on by refinery coke on the refinery coke, has fundamentally eliminated the pollution of refinery mud to environment.But this patent is not open or point out the use delay coking process to handle abandoned biomass.
Therefore, this area presses for a kind of method that can handle abandoned biomass and production biomass energy effectively easily on a large scale of exploitation.
Summary of the invention
Purpose of the present invention just provides a kind of method with delay coking process processing abandoned biomass, and it can handle abandoned biomass and production biomass energy effectively easily on a large scale, has solved problems of the prior art.
The invention provides a kind of method of handling abandoned biomass, it may further comprise the steps:
(a) be 0.1-2mm with abandoned biomass raw material pulverizing to mean particle size;
(b) raw material after will pulverizing mixes with oil, and the mixing quality of wherein said raw material and oil is than being 0.05-15%;
(c) mixed raw material is heated to 190-300 ℃;
(d) described raw material further is heated to 420-510 ℃;
(e) described raw material is carried out delayed coking and handle, obtain coke and oil gas product;
(f) oil gas product to gained carries out fractionation, obtains the fractionation product.
One preferred embodiment in, described abandoned biomass raw material is selected from: husk, stalk, pericarp, fruit stone, fallen leaves, bark, weeds, culled wood, life kitchen are surplus, the waste of difficult degradation in waste paper and the city refuse landfill stale garbage screen overflow.
Another preferred embodiment in, in step (a), be 0.1-1mm with abandoned biomass raw material pulverizing to mean particle size.
Another preferred embodiment in, described grease separation is from residual oil, distillate and their mixture.
Another preferred embodiment in, in step (b), the mixing quality of described raw material and oil is than being 5-15%.
Another preferred embodiment in, in step (c), the described convective heating that is heated to be, its temperature rise rate is 5-10 ℃/minute.
Another preferred embodiment in, in step (c), mixed raw material is heated to 200-240 ℃.
Another preferred embodiment in, in step (d), the described radiation heating that is heated to be, its temperature rise rate are 20-80 ℃/minute.
Another preferred embodiment in, in step (d), described raw material further is heated to 480-500 ℃.
Another preferred embodiment in, in step (e), the working pressure of described delayed coking is the 0.01-0.2MPa gauge pressure.
Description of drawings
Fig. 1 be according to one embodiment of the present invention be the synoptic diagram of the delayed coking treatment scheme of raw material with the abandoned biomass, wherein, digital 1-5 represents following equipment respectively:
1: pulverizer
2: mixing tank
3: process furnace
4: coke drum
5: separation column.
Embodiment
The present inventor finds after having passed through extensive and deep research, by abandoned biomass raw material process is pulverized, and with after residual oil and separation column distillate mix, mixed raw material is carried out two sections heating (described raw material is because temperature rise rate is too fast thereby a small amount of pyrogenic reaction only takes place) in process furnace, the process furnace that then speeds away enters coke drum and carries out cracking and condensation reaction, just can carry out delayed coking to described raw material handles, thereby obtain required product, realized the innoxious on a large scale of abandoned biomass resource, energy is handled, and has enlarged the source of refinery feedstock simultaneously again.
Technical conceive of the present invention is as follows: after abandoned biomass raw material process is pulverized, mix with oil (being selected from residual oil, distillate and their mixture), so that raw material has good flowability and thermal conduction, wherein, described abandoned biomass raw material is about 0.05-15% (preferably about 5-15%) with the mass ratio of oil; Then, with mixed raw material heating (for example, convective heating) to about 190-300 ℃ (preferably about 200-240 ℃), then rapid heating (for example, radiation heating) is to about 420-510 ℃ (preferably about 480-500 ℃); Subsequently described raw material is carried out delayed coking and handle (a small amount of pyrogenic reaction only takes place because temperature rise rate is too fast described raw material), obtain required product, i.e. coke and oil gas; Then.Oil gas product to gained carries out fractionation, obtains further purifying gas product and distillate.
Delay coking process is that a kind of heavy oil lighting technology commonly used in the petroleum refining industry is arranged, and can handle various heavy oil residues, oily sludge etc.The raw material oil composition mainly is alkane, naphthenic hydrocarbon, aromatic hydrocarbons and bituminous matter etc.Delay coking process generates small molecule hydrocarbon and coke with the hydrocarbon molecule of stock oil through deep pyrolytic and condensation reaction.The delay coking process technology maturation, investment is moderate, processing charges is lower, refines oil at home to account for significant proportion in the amount of finish, and the large-scale delayed coking unit treatment capacity of single series can reach ten thousand tons/year of 10-160.
The main component of abandoned biomass comprises carbohydrate (comprising Mierocrystalline cellulose, hemicellulose, xylogen, starch etc.), fat and protein etc., and these materials all can be considered long polymeric carbon chain compound.The present invention utilizes the delayed coking production equipment, makes the reaction of biomass generation high temperature pyrolysis, thereby obtains certain amount of fluid fuel (bio-oil) and coke.Utilize delayed coking unit treatment technology maturation, treatment scale big, can realize that innoxious on a large scale, the energy of abandoned biomass resource handled, enlarged the source of refinery feedstock simultaneously again.
Described abandoned biomass raw material comprises agricultural wastes, for example husk, stalk, pericarp, fruit stone etc.; Forestry waste, for example fallen leaves, bark, weeds, culled wood etc.; And the city organic domestic waste, for example the resident living kitchen is surplus, the waste of difficult degradation in the waste paper, city refuse landfill stale garbage screen overflow etc.
It is 0.1-2mm, preferably 0.1-1mm that described raw material is crushed to mean particle size.
The temperature rise rate of described convective heating is about 5-10 ℃/minute, and preferably about 6-8 ℃/minute, the temperature rise rate of described radiation heating is about 20-80 ℃/minute, preferably about 50-60 ℃/minute.
Below referring to Fig. 1.
Fig. 1 is to be the synoptic diagram of the delayed coking treatment scheme of raw material with the abandoned biomass according to one embodiment of the present invention.With the abandoned biomass raw material send into pulverize in the pulverizer 1 after, send in the mixing tank 2 and mix (wherein with residual oil, distillate, described raw material is 0.05-15% with the mixing quality ratio of oil), then mixed raw material is sent in the convection tubes of process furnace 3, be preheated to after about 190-300 ℃ with about 5-10 ℃/minute temperature rise rate, be transported to again in the radiation chamber boiler tube of process furnace 3, be rapidly heated to about 420-510 ℃ with about 20-80 ℃/minute temperature rise rate.Because temperature rise rate is too fast, raw material has little time to take place coking and just carries by the bottom to coke drum 4.The working pressure of coke drum 4 is 0.01-0.2MPa (gauge pressure), and the raw material after the heating carries out reactions such as cracking, condensation in coke drum 4, generate coke at last.Coke is flocked in the coke drum 4, and the oil gas that reaction produces is overflowed from the cat head of coke drum 4, advances that fractionation obtains gas products and distillate (mainly being gasoline, diesel oil and bio-oil) in people's separation column 5.
Major advantage of the present invention is:
Handle abandoned biomass owing to adopted delayed coking production technique commonly used in the existing petroleum refining industry; reduce secondary pollution and needed the waste of landfill disposal; can realize handling on a large scale abandoned biomass and production biomass energy quickly; realized the minimizing of abandoned biomass, innoxious and recycling treatment, had important and practical meanings for environment protection.
Below, by embodiment the present invention is described in further detail, still, should be appreciated that, in any case the present invention also is not limited to these embodiment.
Embodiment 1
Use fallen leaves as raw material, it is crushed to mean particle size is 0.1mm, send into then in the mixing tank and mix with residual oil, distillate, wherein the mixing quality ratio is 0.05%, then mixed raw material is sent into that the temperature rise rate with 5 ℃/minute is preheated to 190 ℃ in the convection tubes of process furnace, temperature rise rate with 20 ℃/minute is warming up to 420 ℃ rapidly in the radiation chamber boiler tube of process furnace then, and wherein the coke drum working pressure is 0.01MPa (gauge pressure).Reaction also carries out that the distillate productive rate of gained is about 52.1% (butt) after the fractionation, and the productive rate of coke is about 33.6% (butt).
Use culled wood as raw material, it is crushed to mean particle size is 2mm, send into then in the mixing tank and mix with residual oil, distillate, wherein the mixing quality ratio is 15%, then mixed raw material is sent into that the temperature rise rate with 10 ℃/minute is preheated to 300 ℃ in the convection tubes of process furnace, temperature rise rate with 80 ℃/minute is warming up to 510 ℃ rapidly in the radiation chamber boiler tube of process furnace then, and wherein the coke drum working pressure is 0.2MPa (gauge pressure).Reaction also carries out that the distillate productive rate of gained is about 41.2% (butt) after the fractionation, and the productive rate of coke is about 39.4% (butt).
Use stalk as raw material, it is crushed to mean particle size is 0.2mm, send into then in the mixing tank and mix with residual oil, distillate, wherein the mixing quality ratio is 5%, then mixed raw material is sent into that the temperature rise rate with 6 ℃/minute is preheated to 240 ℃ in the convection tubes of process furnace, temperature rise rate with 50 ℃/minute is warming up to 480 ℃ rapidly in the radiation chamber boiler tube of process furnace then, and wherein the coke drum working pressure is 0.03MPa (gauge pressure).Reaction also carries out that the distillate productive rate of gained is about 50.4% (butt) after the fractionation, and the productive rate of coke is about 33.6% (butt).
Embodiment 4
Use waste paper as raw material, it is crushed to mean particle size is 1mm, send into then in the mixing tank and mix with residual oil, distillate, wherein the mixing quality ratio is 14%, then mixed raw material is sent into that the temperature rise rate with 8 ℃/minute is preheated to 280 ℃ in the convection tubes of process furnace, temperature rise rate with 60 ℃/minute is warming up to 500 ℃ rapidly in the radiation chamber boiler tube of process furnace then, and wherein the coke drum working pressure is 0.15MPa (gauge pressure).Reaction also carries out that the distillate productive rate of gained is about 40.1% (butt) after the fractionation, and the productive rate of coke is about 36.9% (butt).
Embodiment 5
The waste that uses difficult degradation in the city refuse landfill stale garbage screen overflow is as raw material, it is crushed to mean particle size is 0.5mm, send into then in the mixing tank and mix with residual oil, distillate, wherein the mixing quality ratio is 5%, then mixed raw material is sent into that the temperature rise rate with 8 ℃/minute is preheated to 280 ℃ in the convection tubes of process furnace, temperature rise rate with 60 ℃/minute is warming up to 500 ℃ rapidly in the radiation chamber boiler tube of process furnace then, and wherein the coke drum working pressure is 0.1MPa (gauge pressure).Reaction also carries out that the distillate productive rate of gained is about 55.1% (butt) after the fractionation, and the productive rate of coke is about 35.1% (butt).
Embodiment 6
Use discarded sawdust as raw material, it is crushed to mean particle size is 0.1mm, sending into mixing tank then mixes with residual oil, distillate, wherein the mixing quality ratio is 10%, then mixed raw material is sent into that the temperature rise rate with 8 ℃/minute is preheated to 200 ℃ in the convection tubes of process furnace, temperature rise rate with 60 ℃/minute is warming up to 500 ℃ rapidly in the radiation chamber boiler tube of process furnace then, and wherein the coke drum working pressure is 0.1MPa (gauge pressure).Reaction also carries out that the distillate productive rate of gained is about 52.1% (butt) after the fractionation, and the productive rate of coke is about 33.0% (butt).
Though for the purpose that is aware and understand, the present invention is described in detail, but after having read present specification, those skilled in the art will be appreciated that, under the prerequisite that does not depart from spirit of the present invention and essence, can carry out various modifications and change to the present invention, these modifications and change all fall within the scope of appended claims.
Claims (10)
1. method of handling abandoned biomass, it may further comprise the steps:
(a) be 0.1-2mm with abandoned biomass raw material pulverizing to mean particle size;
(b) raw material after will pulverizing mixes with oil, and the mixing quality of wherein said raw material and oil is than being 0.05-15%;
(c) mixed raw material is heated to 190-300 ℃;
(d) described raw material further is heated to 420-510 ℃;
(e) described raw material is carried out delayed coking and handle, obtain coke and oil gas product;
(f) oil gas product to gained carries out fractionation, obtains the fractionation product.
2. the method for claim 1, it is characterized in that described abandoned biomass raw material is selected from: husk, stalk, pericarp, fruit stone, fallen leaves, bark, weeds, culled wood, life kitchen are surplus, the waste of difficult degradation in waste paper and the city refuse landfill stale garbage screen overflow.
3. the method for claim 1 is characterized in that, in step (a), is 0.1-1mm with abandoned biomass raw material pulverizing to mean particle size.
4. the method for claim 1 is characterized in that, described grease separation is from residual oil, distillate and their mixture.
5. the method for claim 1 is characterized in that, in step (b), described raw material is 5-15% with the mixing quality ratio of oil.
6. the method for claim 1 is characterized in that, in step (c), and the described convective heating that is heated to be, its temperature rise rate is 5-10 ℃/minute.
7. the method for claim 1 is characterized in that, in step (c), mixed raw material is heated to 200-240 ℃.
8. the method for claim 1 is characterized in that, in step (d), the described radiation heating that is heated to be, its temperature rise rate are 20-80 ℃/minute.
9. the method for claim 1 is characterized in that, in step (d), described raw material further is heated to 480-500 ℃.
10. the method for claim 1 is characterized in that, in step (e), the working pressure of described delayed coking is the 0.01-0.2MPa gauge pressure.
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| CNB2005100275414A CN100386408C (en) | 2005-07-06 | 2005-07-06 | Delayed coking treatment method for waste biomass |
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| CNB2005100275414A CN100386408C (en) | 2005-07-06 | 2005-07-06 | Delayed coking treatment method for waste biomass |
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| CN100386408C true CN100386408C (en) | 2008-05-07 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020826B (en) * | 2007-03-09 | 2010-11-17 | 华东理工大学 | Kitchen refuse coking treatment process and apparatus |
| ES2366252A1 (en) * | 2008-07-31 | 2011-10-18 | Petróleo Brasileiro S.A. Petrobras | Process for production of bio-oil by coprocessing of biomass in a delayed coking unit |
| BRPI0803545A2 (en) * | 2008-07-31 | 2010-06-15 | Petroleo Brasileiro Sa | bio-oil production process by biomass co-processing in delayed coking unit |
| TW201026837A (en) * | 2008-09-17 | 2010-07-16 | Bdi Bio Diesel Internat Ag | Process for obtaining combustibles and fuels, respectively |
| CN101747919B (en) * | 2009-12-31 | 2013-11-27 | 华东理工大学 | Steam decoking method and device of biomass delay coking process |
| CN102260516B (en) * | 2011-06-29 | 2013-06-19 | 高玉玲 | Method for preparing oil by thermally cracking biomass |
| CN106032470B (en) * | 2015-12-04 | 2017-11-28 | 中国石油大学(华东) | A kind of coking method for processing bio oil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1246514A (en) * | 1998-08-27 | 2000-03-08 | 中国石油化工集团公司 | Improved delay coking process |
| CN1465658A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | Method for simutaneously raising treatment quantity and diesel recovery ratio of delay coking apparatus |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1246514A (en) * | 1998-08-27 | 2000-03-08 | 中国石油化工集团公司 | Improved delay coking process |
| CN1465658A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | Method for simutaneously raising treatment quantity and diesel recovery ratio of delay coking apparatus |
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