CN106477831B - A kind of process of sludge classification conversion production liquid fuel - Google Patents
A kind of process of sludge classification conversion production liquid fuel Download PDFInfo
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- CN106477831B CN106477831B CN201610874459.3A CN201610874459A CN106477831B CN 106477831 B CN106477831 B CN 106477831B CN 201610874459 A CN201610874459 A CN 201610874459A CN 106477831 B CN106477831 B CN 106477831B
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- sludge
- solvent
- liquid fuel
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- extraction
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/002—Sludge treatment using liquids immiscible with water
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/04—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by extraction
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Treatment Of Sludge (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses the processes that a kind of sludge classification converts production liquid fuel, comprising the following steps: carries out extraction after mixing sludge in proportion with solvent 1 at a certain temperature and reacts, obtains gas 1, extraction liquid phase mixture and extraction residue after separation；Liquid phase mixture is extracted mutually to be distilled to obtain solvent 1 and light oil 1 through mutually isolated oil phase and water phase, oil；Water phase, extraction residue, catalysts and solvents 2 carry out liquefaction reaction under certain condition, are isolated to gas 2, solvent 2, light oil 2, heavy oil and residue.The present invention first directly extracts the lightweight organic component in sludge as liquid fuel under the conditions of mild temperature and pressure；Secondly the water phase and residue mixing generated after under the conditions of higher temperature and pressure by extraction carries out liquefaction reaction and further generates liquid fuel, the organic matter fraction in sludge is carried out by separation and staged conversion by two step approach, finally obtains the liquid fuel of high added value.
Description
Technical field
The present invention relates to a kind of technologies that sludge classification is converted to production liquid fuel, belong to recycling sludge using neck
Domain.
Background technique
Sludge is the product after sewage treatment, is that one kind is made of organic debris, microorganism, inorganic particle and colloid etc.
Extremely complex Inhomogeneous charge object, have that organic matter and water content are high, content of beary metal is high and harmful microorganism content is high
The characteristics of.China's sludge disposal technology lags behind always corresponding sewage disposal technology at present, since a large amount of sewage is through handling
Become sludge afterwards, pollution root is not dealt carefully with.The processing mode of sludge still based on traditional landfill or burning,
Secondary environmental pollution is easily caused, and the organic matter of high added value in sludge can not be able to resource utilization.From technological layer
It says, China's specific resistance to filtration does not consider then too much primary concern is that stabilized scope, and in terms of resource utilization.
For " pollutant " resource utilization using the trend for being future development, sludge is sewage treatment overall process resource reclaim in sewage sludge
The key utilized, so the resourcable transformation of sludge will become the important technical of Treatment of Sludge during " 13 ".
At present in terms of recycling sludge trans-utilization there are the problem of can be summarized as two o'clock: one, resourcable transformation cost
It is high, lack effective process flow, and process implementing difficulty is higher, cause resourcable transformation project investment compared with
It is high；Two, product price is low, and existing recycling sludge conversion process products obtained therefrom added value is low, can not be by improving income come more
Mend the income of Treatment of Sludge enterprise.Therefore blowdown enterprise can not be made to form a low cost, the sludge treatment mode of high production, thus
Many blowdown enterprises hang back to sludge treatment.How recycling sludge to be disposed, is come with the income of recycling sludge product
Support sludge treatment cost, enterprise brings certain economic benefit while disposing sludge, then can widely be connect
By.
Patent CN102557366A discloses a kind of processing method of sludge, be pyrolyzed to sludge using supercritical water anti-
It answers, the product after reaction obtains oil product after separation.Since the temperature and pressure condition of this method supercritical water is harsh, for work
The requirement of industry Continuous Running Equipment material is very high, expensive, increases the cost of investment, is unfavorable for the actual industrial of this method
Change application.
The patent ZL201310659027.7 of this seminar exploitation has invented a kind of processing method of sludge, using high temperature height
Pressure hydrothermal liquefaction method converts the organic matter in sludge, and product obtains oil product after separation.Due to the hydro-thermal of this method
Liquefaction reaction is to carry out under the high temperature conditions, easily causes the small molecule organic matter in sludge and cracking occurs and generates gas production
Object causes the yield of major product oil to reduce, to influence economic benefit.
Therefore, there is an urgent need to a kind of more effective processes for converting recycling sludge at present.This process compared with
Use the method for extraction by the small molecule organic matter in sludge under low temperature (being lower than 300 DEG C) and lower pressure (being lower than 15MPa)
It extracts, avoids under the conditions of subsequent high temperature hydrothermal liquefaction that it is cracked, be conducive to improve total oil yield；In addition, extracting
Elimination reaction occurs for the heteroatom functional group during taking in sludge organic matter, reduces subsequent high temperature hydrothermal liquefaction removing impurities atom
Load, be conducive to the raising of oil quality.In conclusion this process has, process conditions are not harsh, operation is simple, set
It is standby the features such as investing low and product yield and high quality, great to have industrial applications prospect.
Summary of the invention
The purpose of the present invention is the organic matter fraction in sludge is carried out separation and staged conversion by two step approach, finally
Obtain the liquid fuel of high added value.
The present invention adopts the following technical scheme:
A kind of process of sludge classification conversion production liquid fuel, which is characterized in that the method are as follows: first will
Lightweight organic component in sludge is directly extracted as liquid fuel, then uses liquefied method by the heavy in sludge
Organic component is converted into light components as liquid fuel, to reach the staged conversion of sludge organic matter；The method includes
Following steps:
1) sludge raw material and solvent 1 mix in mass ratio is made into slurry, wherein solvent 1: sludge raw material=(0.1:1)~
(10:1)；
2) it is filled with extraction atmosphere mixing in the slurry obtained by step 1), is extracted under 50~300 DEG C, normal pressure to 15MPa
It negates and answers, obtain gas 1, extraction liquid-solid mixture, obtain oily phase, water phase and extraction after filtering, separating and extracting liquid-solid mixture
Residue, gas 1 recycle；
3) distilled oil phase is isolated solvent 1 and is recycled, obtains light oil 1；
4) water phase, extraction residue, solvent 2 and catalyst mix in mass ratio, are filled with liquefaction atmosphere, in 300-450 DEG C,
Liquefaction reaction is carried out under 10MPa~25MPa, wherein water phase: extraction residue=(10:1)~(0:1), solvent 2: extraction residue=
The quality of (10:1)~(0:1), water phase and solvent 2 must not be 0 simultaneously, and catalyst loading accounts for the mass ratio model of extraction residue
It encloses for 0-10%；
5) liquefaction products obtain gas 2, solvent 2, light oil 2, heavy oil and residue after separation, and solvent 2 recycles, gas
2 parts recycle.
The sludge raw material is urban domestic wastewater sludge, plant produced wastewater sludge or their mixture (including height
Aqueous organic waste slurry), above-mentioned sludge need not be dried.
The solvent 1 is polar organic solvent, non-polar organic solvent, hydrogen supply dissolvent or their mixed solvent.
The solvent 2 is water, polar organic solvent, non-polar organic solvent, hydrogen supply organic solvent or their mixing
Solvent.
The polar organic solvent is selected from methanol, ethyl alcohol, propyl alcohol, isopropanol, acetic acid, ether, acetone, tetrahydro furan
It mutters, one of chloroform isopolarity organic solvent.
The non-polar organic solvent is selected from benzene, toluene, n-hexane, methylene chloride, carbon tetrachloride, carbon disulfide etc.
One of non-polar organic solvent；
The hydrogen supply dissolvent is one in the hydrogen supply dissolvent that the condensed-nuclei aromatics partial hydrogenation such as naphthalene, anthracene and phenanthrene generates
Kind.
The extraction atmosphere be selected from one of inert atmosphere, oxidizing atmosphere or reducing atmosphere,
The liquefaction atmosphere is selected from one of inert atmosphere, oxidizing atmosphere or reducing atmosphere；
The inert atmosphere is nitrogen, and oxidizing atmosphere is oxygen or air, reducing atmosphere CO, H2Or synthesis gas
One of.
The gas 1 be include CO, CO2、H2、CH4And a small amount of C2-C4Hydrocarbon gas and micro H2S and NH3Mixing
Gas.
The light oil 1 is the organic matter for being dissolved in solvent 1 that sludge generates after extracting.
The gas 2 is mainly including CO, CO2、H2、CH4And a small amount of C2-C4Hydrocarbon gas and micro contain S or N
Gaseous impurity mixed gas.
The light oil 2 be extraction residue in organic matter through hydrothermal liquefaction convert and generate dissolve in the organic of n-hexane
Object.
The catalyst is compound selected from metal Fe, Co, Mo, Ni, one in alkalies and alkaline earth compound
Kind is several.
The extraction time and liquefying time is 30-120min.
The present invention has the advantages that the sludge of resourcable transformation sewage treatment plant；Organic matter fraction in sludge carries out energy
Sourceization utilizes, the liquid fuel as high attached value；To raw sludge without particular/special requirement.It embodies are as follows: usual for sludge
Humic acid, protein and carbohydrate rich in, wherein quite a few dissolves in specific organic solvent, therefore first
Organic extraction process is first passed through, the higher organic solvent soluble constituent of added value in sludge is separated, it is simultaneous to can avoid this portion
Substance (this moieties is extremely easy in decomposition as micro-molecular gas under liquefaction condition) is divided to be converted into subsequent liquefaction reaction attached
Value added low gaseous by-product；After extraction, 90% or more water is transferred in water phase in sludge, realizes water in sludge
Separation, and containing compounds such as a large amount of acid, alcohol, aldehyde in the water phase, it is the suitable component of later liquefaction solvent；It is remained after extraction
Remaining water phase and residue carry out direct liquefaction reaction, realize the bigger molecule organic matter in water phase in organic matter and extraction residue
It is converted into the high liquid fuel of added value together；After above-mentioned extraction and liquefaction reaction, most organic is obtained in sludge
To be converted into liquid fuel, content of organics is extremely low in residual residue, can be directly used as the original of brickmaking or production cement etc.
Material, to realize the target of recycling sludge utilization and zero-emission.
Detailed description of the invention
Fig. 1 is specific flow chart of the invention, while being also the schematic diagram of a specific embodiment of the invention.
Specific embodiment
Embodiment
For a further understanding of the features of the present invention and property, the invention will be further described with reference to embodiments,
But the present invention is not limited to these embodiments.Sludge in embodiment is sludge (its of Shanghai Shi Dongkou sewage treatment plant
1) Industrial Analysis and elemental analysis the results are shown in Table, other sludge also have similar composition.
The Industrial Analysis and elemental analysis of 1 raw sludge of table
* minusing obtains
Embodiment 1: accurately weighing 100g raw sludge and 300g n-hexane, is uniformly mixed and forms slurry, is added to autoclave
In reactor, after nitrogen displacement, temperature of reactor is increased to 300 DEG C (reaction pressure 11.3MPa), is extracted under this condition
30min；After extraction, gas 1 and extraction liquid-solid mixture are obtained, grease liquid mixture is obtained by filtration in liquid-solid mixture
And extraction residue；Oil water mixture is mutually separated, obtains oily phase and water phase, and oil is mutually subjected to distillation and handles to obtain light oil
1 and n-hexane；Water phase and extraction residue are transferred in tank reactor, 1gNa is added2CO3With 100g tetrahydrofuran, it is filled with
Then reactor is risen to 300 DEG C (reaction pressure 15.1MPa), liquefaction reaction 30min by the CO gas of 4MPa；Liquefaction reaction knot
Shu Hou, obtains gas 2 and liquid-solid mixture, and liquid-solid mixture obtains water, light oil 2, tetrahydrofuran, heavy oil and residual after separation
Slag.
Wherein, gas 1 be include CO, CO2、H2、CH4And a small amount of C2-C4Hydrocarbon gas and micro H2S and NH3Mixing
Gas.
Light oil 1 is the organic matter for being dissolved in solvent 1 that sludge generates after extracting.
Gas 2 is mainly including CO, CO2、H2And CH4And a small amount of C2-C4Hydrocarbon gas and the micro gas containing S or N
The mixed gas of impurity.
Light oil 2 is the soluble organic matter of n-hexane that organic matter is generated through hydrothermal liquefaction conversion in extraction residue.
Embodiment 2~6: similar operations are carried out with embodiment 1, in addition to reaction condition, solvent 1, solvent 2 and catalyst also have
Institute is different, other steps are the same.
The reaction condition of Examples 1 to 6 and it the results are shown in Table 2.
The reaction condition and result of 2 Examples 1 to 6 of table
※Above-mentioned products collection efficiency is on the basis of moisture-and-ash-free basis sludge quality
By embodiment as it can be seen that the present invention has recycled most organic matters in sludge, the liquid fuel of high added value is obtained,
Realize sewage sludge harmlessness, minimizing, energy and resource utilization.
Claims (5)
1. a kind of process of sludge classification conversion production liquid fuel, which is characterized in that the method are as follows: first will be dirty
Lightweight organic component in mud is directly extracted as liquid fuel, is then had the heavy in sludge using liquefied method
Machine component is converted into light components as liquid fuel, to reach the staged conversion of sludge organic matter；The method includes such as
Lower step:
1) sludge raw material and solvent 1 mix in mass ratio is made into slurry, wherein solvent 1: sludge raw material=(0.1:1)~(10:
1)；
2) it is filled with extraction atmosphere mixing in the slurry obtained by step 1), carries out extracting under 50~300 DEG C, normal pressure to 15MPa anti-
It answers, obtains gas 1, extraction liquid-solid mixture, obtain oily phase, water phase and extraction residue after filtering, separating and extracting liquid-solid mixture,
Gas 1 recycles；
3) distilled oil phase is isolated solvent 1 and is recycled, obtains light oil 1；
4) water phase, extraction residue, solvent 2 and catalyst mix in mass ratio, are filled with liquefaction atmosphere, in 300-450 DEG C, 10MPa
Liquefaction reaction is carried out under~25MPa, wherein water phase: extraction residue=(10:1)~(0:1), solvent 2: extraction residue=(10:
1) quality of~(0:1), water phase and solvent 2 must not be 0 simultaneously, and the mass ratio range that catalyst loading accounts for extraction residue is
0-10%；
5) liquefaction products obtain gas 2, solvent 2, light oil 2, heavy oil and residue after separation, and solvent 2 recycles, and gas 2
Divide and recycles；
Wherein, gas 1 be include CO, CO2、H2、CH4And a small amount of C2-C4Hydrocarbon gas and micro H2S and NH3Mixed gas；
Light oil 1 is the organic matter for being dissolved in solvent 1 that sludge generates after extracting；Gas 2 is mainly including CO, CO2、H2、CH4, and it is a small amount of
C2-C4The mixed gas of hydrocarbon gas and the micro gaseous impurity containing S or N；Light oil 2 is organic matter in extraction residue through water
The organic matter for dissolving in n-hexane of hydrothermal solutionization conversion and generation；Solvent 1 is polar organic solvent, non-polar organic solvent, confession
Hydrogen solvent or their mixed solvent；Solvent 2 be water, polar organic solvent, non-polar organic solvent, hydrogen supply dissolvent or they
Mixed solvent；
The polar organic solvent is selected from methanol, ethyl alcohol, propyl alcohol, isopropanol, acetic acid, ether, acetone, tetrahydrofuran, chlorine
One of imitate；
The non-polar organic solvent is one in benzene, toluene, n-hexane, methylene chloride, carbon tetrachloride, carbon disulfide
Kind；
The hydrogen supply dissolvent is one of the hydrogen supply dissolvent that the condensed-nuclei aromatics partial hydrogenation selected from naphthalene, anthracene and phenanthrene generates.
2. the process of sludge classification conversion production liquid fuel as described in claim 1, which is characterized in that the sludge
Raw material is urban domestic wastewater sludge, plant produced wastewater sludge or their mixture.
3. the process of sludge classification conversion production liquid fuel as described in claim 1, which is characterized in that the extraction
Taking atmosphere is selected from one of inert atmosphere, oxidizing atmosphere or reducing atmosphere, and the liquefaction atmosphere is selected from inertia
One of atmosphere, oxidizing atmosphere or reducing atmosphere.
4. the process of sludge classification conversion production liquid fuel as claimed in claim 3, which is characterized in that described is lazy
Property atmosphere be nitrogen, oxidizing atmosphere be oxygen or air, reducing atmosphere CO, H2Or one of synthesis gas.
5. the process of sludge classification conversion production liquid fuel as described in claim 1, which is characterized in that described urges
Agent is compound selected from metal Fe, Co, Mo, Ni, one or more of in alkalies and alkaline earth compound.
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| CN107265799B (en) * | 2017-06-30 | 2023-11-17 | 南充西南石油大学设计研究院有限责任公司 | Comprehensive treatment process and device for oily solid waste |
| CN107858170B (en) * | 2017-11-14 | 2020-02-11 | 沈阳航空航天大学 | CO (carbon monoxide) 2Method for preparing bio-oil by two-step grading hydrothermal liquefaction of lignocellulose under atmosphere |
| CN110395857A (en) * | 2018-04-19 | 2019-11-01 | 北京中科国通环保工程技术股份有限公司 | The method and apparatus for handling oil-containing hydrous matter |
| CN110862205A (en) * | 2019-12-23 | 2020-03-06 | 智慧化净资源环境科技(辽宁省)有限公司 | Oil sludge separation device and separation method |
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| CN102836666A (en) * | 2012-09-21 | 2012-12-26 | 深圳市仁金新能源发展有限公司 | Method and equipment for industrially producing clean liquid fuel by utilizing household waste or sludge press water |
| CN103614168A (en) * | 2013-12-09 | 2014-03-05 | 华东理工大学 | Processing method for preparing liquid fuel by performing sludge liquefaction |
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| US7998351B2 (en) * | 2006-12-22 | 2011-08-16 | Vinod Kumar Rai | Tannin based polymeric coagulants composition and method of use |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102836666A (en) * | 2012-09-21 | 2012-12-26 | 深圳市仁金新能源发展有限公司 | Method and equipment for industrially producing clean liquid fuel by utilizing household waste or sludge press water |
| CN103614168A (en) * | 2013-12-09 | 2014-03-05 | 华东理工大学 | Processing method for preparing liquid fuel by performing sludge liquefaction |
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