CN102557366B - Sludge treatment method and application thereof - Google Patents

Sludge treatment method and application thereof Download PDF

Info

Publication number
CN102557366B
CN102557366B CN201210003882.8A CN201210003882A CN102557366B CN 102557366 B CN102557366 B CN 102557366B CN 201210003882 A CN201210003882 A CN 201210003882A CN 102557366 B CN102557366 B CN 102557366B
Authority
CN
China
Prior art keywords
mud
sludge treatment
sludge
oil
reaction
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
Application number
CN201210003882.8A
Other languages
Chinese (zh)
Other versions
CN102557366A (en
Inventor
宋庆峰
程乐明
曹雅琴
杜娟
高志远
宋成才
张玉宝
田文堂
谷蔚
赵晓
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Environmental Protection Technology Co., Ltd.
Original Assignee
ENN Science and Technology Development Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by ENN Science and Technology Development Co Ltd filed Critical ENN Science and Technology Development Co Ltd
Priority to CN201210003882.8A priority Critical patent/CN102557366B/en
Publication of CN102557366A publication Critical patent/CN102557366A/en
Application granted granted Critical
Publication of CN102557366B publication Critical patent/CN102557366B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention relates to a sludge treatment method for preparing oil products by liquefying sludge. The method comprises the step of performing liquefaction on the sludge in the subcritical or supercritical state of water to obtain the oil products. In addition, the invention also relates to application of the sludge treatment method to sludge treatment.

Description

Method for sludge treatment and application thereof
Technical field
The present invention relates to a kind of method for sludge treatment and application thereof, mud carried out liquefying under the condition of certain temperature and pressure in particular to comprising and prepares the application in sludge treatment of the method for sludge treatment of oil product and the method.
Background technology
In recent years, the generation of China's municipal sludge continues to increase, according to " about building national urban wastewater treatment facility fourth quarter in 2010 and the circular of running condition ", ended for the end of the year 2010, China's urban wastewater treatment amount reaches 343 billion cubic meters, and the sludge quantity produced in sewage treatment process also increases considerably.Within 2010, national mud turnout is about 2,199 ten thousand tons, produces 6.02 ten thousand tons, mud every day.According to current tempo, to 2015 end of the years, China's mud annual production arrives 2,615 ten thousand tons to major general, daily output about 7.2 ten thousand tons, mud.The minimizing process of mud and Appropriate application have been very serious problems.
Usually, the unprocessed front water content of municipal sludge is up to 99%, and after the drying and other treatment such as press filtration, water content is about 80%, and containing heavy metal (as Co, Pb, Ni etc.).Meta-bolitess at different levels containing a large amount of protein, fat, mineral oil, washing composition, soil ulmin, bacterium and bacterium in the organic composition of mud, wherein also contains parasite or ovum, microorganism, the residue of some industrial macromolecular materials, waste oil paint, the remnants of various organic solvent, organic Jiao or incomplete decomposing thing.
The general treatment process of mud is landfill and burning, there are problems.Such as, traditional sludge incineration processing scheme, is mostly first collected and add a large amount of combustiblematerialss after dehydrating process again by mud to ignite, puts into incinerator and burn.This burning mode is on the one hand because sludge calorific value is lower; and moisture content is large; cause fire box temperature low; insufficient callable heat that burns is also few; so also higher with the calorific value such as coal, refinery coke fuel blending burns usually; also have the insufficient solid residue of more burning after burning, contain a large amount of oxysulfide, oxynitride and dioxin toxic and harmful in the middle of tail gas simultaneously, all detrimentally affect is produced to air, HUMAN HEALTH.
Being developed the method for sludge gasification afterwards, is H by organic matter transformation 2, CH 4, CO, CO 2deng gas, be separated further and can obtain industrial chemicals.
In Chinese patent application CN1405103A, disclose a kind for the treatment of process of mud, its technology mainly adopted is that the chemical oxidation in traditional sludge treatment technique is replaced with wet oxidation, and it is CO that object is the Organic oxidation in mud 2, N 2or oxynitride, dewatering is improved greatly, organic toxicity can also be removed simultaneously.But do not realize organic effective utilization.
In Chinese patent application CN101705105A, disclose a kind of biomass liquefied oil and preparation method thereof, its disclosure is by pyrolyzing sludge, the method obtaining biomass liquefied oil.The method mainly adopts high temperature by pyrolyzing sludge, obtains biomass liquefied oil therefrom, but what adopt in the method is normal pressure, the utilization ratio of the organic substance therefore in mud is extremely low, and operating process needs to carry out in reducing atmosphere or inert atmosphere, adds running cost and operation easier.In addition, the residence time of its technique is long, and the processing power of unit time is low.
Therefore, at present in the urgent need to a kind of organic substance in mud is changed into oil product and effectively utilize more fully, method that simultaneously energy consumption is smaller.
Summary of the invention
In order to solve the problem, the present inventor conducts in-depth research, found that, by making it react under specific temperature and pressure in mud, organic substance in mud can be prepared into oil product, oil product yield is high, thus not only reduces the amount of mud, but also fully the organic substance in mud is fully recycled, achieve the recycling of refuse.In addition; advantage of the present invention is also that the reaction times is very short; and technological process does not need reducing atmosphere or inert atmosphere protection, the simultaneously energy consumption of method of the present invention smaller, is conducive to application industrially, reaches the object that the present application will realize thus.
As everyone knows, material can the state such as solid-state, liquid, gaseous state and supercritical state exist, and the state residing for material depends on its state parameter such as temperature, pressure, density, composition.When the temperature and pressure of material is simultaneously higher than its critical temperature and emergent pressure, then it is claimed to be in supercritical state.Supercritical state is different from gaseous state and liquid state, and it has special physicochemical property.Supercritical water is the one of supercutical fluid.When temperature is higher than 374.1 DEG C, pressure is higher than (pressure described herein is absolute pressure, lower same) during 22.12MPa, and water is in supercritical state, and its character there occurs very large change.Such as, under non-supercritical state, basic metal or alkaline earth metal hydroxides or basic metal or alkaline earth metal carbonate usually have good solubility in water, but in the water close to above-critical state and supercritical state, their solubleness will sharply reduce, so that can separate out from its aqueous solution, the solubleness of salt in overcritical reduces greatly.In addition, under supercritical state, the specific inductivity of water reduces, and polarity weakens, and this makes it closer to organism, therefore has good solvency action to organic matter, and it also has excellent mass transfer ability simultaneously, is a kind of desirable reaction medium.
The present invention relates to a kind of method for sludge treatment, the method comprises: mud is carried out liquefaction reaction under the subcritical of water or supercritical state, obtains oil product thus.Subcritical or the supercritical state of described water refers to that temperature is 330 ~ 480 DEG C, pressure is 15 ~ 30MPa.The described mud as raw material does not limit by special, can be directly from the mud of factory, hospital or municipal administration etc., but preferably purify it before carrying out reaction.Such as first the mud from factory, hospital or municipal administration etc. is purified, to remove inorganic substance wherein, then the mud after purification is used for liquefaction reaction.Purification can adopt any known method, such as gravity settling desanding.Mud preferably containing at least one element in iron, cobalt, nickel, molybdenum.
In addition, for the mud used as raw material in the present application, wherein the content of water is not particularly limited, but preferred water-content is 65 ~ 99wt% usually, can be regulated by the conventional water-content of method to mud.
Under the specified conditions of above-mentioned temperature and pressure, water in mud is in subcritical or supercritical state, other composition in mud is had an effect, make the organic substance in mud and inorganic substance etc. start to occur the chemical reaction of pyrolysis, reformation, conversion etc., thus change into gas, the oil product of liquid and solids.In addition, in mud, itself contains the metallic element of iron, cobalt, nickel, molybdenum etc., these metallic elements or their compound also have certain katalysis, further enhance mud liquefaction yield under this condition thus.
In the methods described above, as mentioned above, the organic substance in mud is by the decomposition under above-mentioned specific condition and reformation, and major part changes into the liquid product with high added value, i.e. oil product.
In addition, in aforesaid method, as mud liquefaction raw material and sludge components in component such as water, inorganic substance and organic substance, be not particularly limited, but the concentration of preferred described sludge solids is 1 ~ 35wt%.As required, the part water that also can add in the forward direction mud carrying out mud liquefaction reaction in other water or removing mud carrys out the concentration of conditioning of mud.
In above-mentioned mud liquefaction reaction, temperature of reaction preferably 380 ~ 450 DEG C further, to improve the yield of liquid product and oil product.Reaction times can be determined according to concrete practical situation, but preferably the liquefaction reaction time is 1 ~ 60 minute, more preferably 5 ~ 15 minutes.
In the method for sludge treatment of the invention described above, the product that wherein mud post liquefaction obtains comprises oil product, solid residue, moisture and synthetic gas.Product, after cooling, being separated, obtains petroleum naphtha, petrol and diesel oil and oil fuel respectively by oil product.Petroleum naphtha is generally the general term of a part of oil lighting end, distillation boiling range is at 30 ~ 200 DEG C, and in method of the present invention, the chemical composition that mud liquefaction process produces mostly is hydrocarbons, close with the clear cut of oil, therefore define light constituent wherein with petroleum naphtha.Same reason, boiling range is defined as petrol and diesel oil the component of 200 ~ 370 DEG C; The component of boiling point more than 370 DEG C is defined as oil fuel.Described herein is cooled to cool to room temperature.Described separation can be common separation means, such as, distill cutting, rectified purified, purification etc.
In addition, in above-mentioned mud liquefaction reaction, catalyzer can be added as required, improve the yield that mud is converted into oil product further thus.The metallic element of iron, cobalt, nickel or the molybdenum etc. that mostly itself contain in the middle of above-mentioned mud or their compound, under this state of arts, also have certain katalysis, further enhance mud liquefaction yield under this condition thus.
In addition, the invention still further relates to the application adopting above-mentioned method for sludge treatment lignin-sludge.
Effect of the present invention
According to the present invention, by mud is carried out liquefaction reaction under given conditions, obtain the oil product being rich in various oil, the method not only can carry out minimizing process and harmless treatment to mud, also achieves the recycling of sludge waste simultaneously.Supercritical water or subcritical water, owing to having special physicochemical property, greatly increase mass transfer and rate of heat transfer, and mud raw material under these conditions, greatly accelerate by speed of response, and be conducive to produce liquid oil product.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of a specific embodiment of the present invention.
Embodiment
Below, applicant is described in detail with reference to accompanying drawing 1 pair of embodiments of the present invention.But the present invention is not limited to which.
First, the primary sludge raw material from municipal administration, hospital or factory (such as chemical plant etc.) is purified, is then joined in reactive system.This reactive system can comprise reactor and interchanger or well heater, mud carries out liquefaction reaction at reactive system, and the product obtained after reaction comprises gas, liquid and solid, then enters separation system to be separated, after separation system, gas, liquid, solid are separated.Wherein gaseous combustible burns heat release, and by the energy transport of release to reactive system, or isolated H 2be circulated back to liquefying reactor to participate in carrying out liquefaction reaction, H 2the synthetic gas produced when both can be derived from liquefaction, also can supplement in addition; Use can be waited as building employing as obtaining solids after above-mentioned separation.And the liquid obtained is through process further, chemical can be obtained.
In above-mentioned method for sludge treatment, mud liquefaction reaction concrete steps are as follows.First heat liquefying reactor, pressurize, make temperature of reaction be 330-480 DEG C, preferred 380-450 DEG C, reaction pressure is 15-30Mpa, and under such temperature and pressure condition, water is in subcritical or supercritical state.Under the above-described reaction conditions, mud starts the chemical reactions such as pyrolysis, reformation, conversion occur, in mud, itself is containing metallic elements such as iron, cobalt, nickel, molybdenums, the compound of these elements or these elements also has certain katalysis, can strengthen the liquefaction yield of mud thus further.Controlling the reaction times is 1 ~ 60 minute, preferably 5 ~ 15 minutes.Generation comprises the reaction product of oil product (this oil product is gaseous state at reaction conditions), and by-product synthetic gas and residue.Oil product is joined in refrigerating unit and carry out refrigerated separation, obtain liquid oil product and the synthetic gas of gaseous state.Again the fluid oil obtained is separated, such as, distills, cut suitable cut, finally obtain petroleum naphtha, petrol and diesel oil and oil fuel.Synthetic gas then can be used for other industrial use, such as, for preparing piped gas, or, can from this synthetic gas recover hydrogen, and the hydrogen of recovery turned back in reactor use as raw material.Residue can use as material of construction through processing further.
Embodiment
Below by way of enumerating embodiment to further describe the present invention.But the present invention is not limited to these embodiments.It should be noted that at this, the mud in embodiment is the municipal sludge of Zhengzhou City, and the analysis of its mud is as shown in table 1.The municipal sludge in other areas has similar composition.
The technical analysis of table 1 mud and ultimate analysis
Embodiment 1
By gravity settling desanding, after the raw sludge from municipal mud being purified, forming sludge concentration is the slurry of 15wt%.Then join in reactor by this slurry, control reactor for temperature 350 DEG C, reaction pressure 17.0MPa, makes sludge reaction 10 minutes under this condition.
After above-mentioned reaction terminates, reactant is taken out from reactor, cooling, then distills, obtains liquid product and oil product, Agilent gas chromatography mass spectrometer is adopted to be measured by this liquid product, result is known, in this product, the content of petroleum naphtha is 52wt%, the content of petrol and diesel oil is the content of 28wt% and oil fuel is 20wt%, and all the other are various impurity.The reaction conditions of this embodiment and obtained by said determination the results are shown in table 3.
The boiling range of each product is as shown in table 2:
Table 2 product boiling range table
Embodiment 2 ~ 16
Embodiment 2 ~ 16 is carried out, except reaction conditions is different with operation similar to Example 1.Its concrete reaction conditions and reaction result are as shown in table 3.1-3.3.
Comparative example 1 ~ 3
Example 1 ~ 3 is compared, except reaction conditions is different with operation similar to Example 1.Its concrete reaction conditions and reaction result are as shown in table 3.4.
The reaction conditions of table 3.1 embodiment 1-4 and reaction result
Note: *oil product yield is the mass percent that oil product accounts for moisture-and-ash-free basis raw material;
*product slates is the percentage ratio that each component in oil product accounts for oil product gross weight
The reaction conditions of table 3.2 embodiment 5 ~ 8 and reaction result
The reaction conditions of table 3.3 embodiment 9 ~ 13 and reaction result
The reaction conditions of table 3.4 comparative example 1 ~ 3 and reaction result
Can be clear that by the above embodiments, outside DEG C temperature of reaction of 330 ~ 480 described in the present application, such as, in comparative example 1 and 2, the temperature of its reaction is respectively 300 DEG C and 500 DEG C, outside scope of the present invention, can be clear that by above-mentioned table 3.4, the yield of the oil product in this comparative example 1 ~ 2 is very low (being respectively 2.5wt% and 5.7wt%).And, even if temperature is in above-mentioned scope, if reaction pressure is outside above-mentioned scope, such as comparative example 3, its pressure adopted is 35MPa, such as, although total oil product yield is increased, compared with embodiment 13, the yield of oil product only improve only 1.7wt%, but it, owing to adopting higher pressure condition, therefore needs high-tension apparatus, and makes energy consumption obviously increase, cost raises, and this is very disadvantageous for industrial utilization.

Claims (7)

1., by a method for sludge treatment for oil product being prepared by mud liquefaction, it comprises the following steps:
Oil product is obtained by mud being carried out under the subcritical of water or supercritical state liquefaction reaction, sludge concentration is 1 ~ 25%, subcritical or the supercritical state of described water refers to that temperature is 380 ~ 450 DEG C, pressure is 15 ~ 30MPa, containing at least one element in iron, cobalt, nickel, molybdenum in described mud.
2. method for sludge treatment as claimed in claim 1, is characterized in that, described mud is purify the rear mud obtained by carrying out from factory or municipal mud.
3. method for sludge treatment according to claim 1, is characterized in that, the time of liquefaction reaction is 1 ~ 60 minute.
4. method for sludge treatment according to claim 1, is characterized in that, the time of liquefaction reaction is 5 ~ 15 minutes.
5. the method for sludge treatment according to any one of claims 1 to 3, is characterized in that, described oil product comprises petroleum naphtha, petrol and diesel oil and oil fuel.
6. the method for sludge treatment according to any one of claims 1 to 3, is characterized in that, after described oil product cooling, being separated, obtains petroleum naphtha, petrol and diesel oil and oil fuel respectively.
7. the application of the method for sludge treatment described in claim 1 ~ 6 in lignin-sludge.
CN201210003882.8A 2012-01-09 2012-01-09 Sludge treatment method and application thereof Active CN102557366B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210003882.8A CN102557366B (en) 2012-01-09 2012-01-09 Sludge treatment method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210003882.8A CN102557366B (en) 2012-01-09 2012-01-09 Sludge treatment method and application thereof

Publications (2)

Publication Number Publication Date
CN102557366A CN102557366A (en) 2012-07-11
CN102557366B true CN102557366B (en) 2015-06-10

Family

ID=46404185

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210003882.8A Active CN102557366B (en) 2012-01-09 2012-01-09 Sludge treatment method and application thereof

Country Status (1)

Country Link
CN (1) CN102557366B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102911691A (en) * 2012-11-05 2013-02-06 天津大学 Method for preparing bio-oil through supercritical pyrolysis of civil sludge
CN103614168B (en) * 2013-12-09 2016-01-20 华东理工大学 The processing method of liquid fuel is prepared in a kind of mud liquefaction
CN104593116B (en) * 2015-01-30 2017-01-04 湖南大学 Biomass liquefying residue prepares the method for solid molding fuel
CN104961310A (en) * 2015-07-09 2015-10-07 周宗南 Method and device for modifying organic sludge to prepare fuel oil
CN105036501B (en) * 2015-08-05 2017-05-03 新奥科技发展有限公司 Sludge degradation treatment method
CN106753461B (en) * 2016-11-22 2019-10-01 新奥生态环境治理有限公司 By the method for municipal refuse hydro-thermal charing process under undercritical conditions
CN107746723B (en) * 2017-11-06 2020-04-10 沈阳航空航天大学 Method for preparing biofuel by liquefying sludge
CN111606547A (en) * 2020-04-17 2020-09-01 路德环境科技股份有限公司 Municipal sludge treatment method and equipment

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101327908A (en) * 2008-07-10 2008-12-24 中国兵器工业第五二研究所 Method for using sludge in supercritical water for preparing hydrogen-rich gas by continuous catalysis gasification

Also Published As

Publication number Publication date
CN102557366A (en) 2012-07-11

Similar Documents

Publication Publication Date Title
CN102557366B (en) Sludge treatment method and application thereof
EP1315784B1 (en) Process for the production of liquid fuels from biomass
Sdrula A study using classical or membrane separation in the biodiesel process
Su et al. Hydrothermal carbonization of food waste after oil extraction pre-treatment: Study on hydrochar fuel characteristics, combustion behavior, and removal behavior of sodium and potassium
CN103172245B (en) Method for quick pyrolysis treatment and in situ conversion product utilization of sludge
CN104355519A (en) Comprehensive sludge treating method based on hydrothermal carbonization and fast microwave pyrolysis
CN105542808A (en) All-closed zero-emission household refuse energy regeneration and comprehensive utilization production process
CN102875005A (en) Sludge biological carbonizing technology based on hydrothermal reaction
JP2011514403A (en) Complete liquefaction of lignocellulosic agricultural waste to form liquid biofuels
CN103449701A (en) Method and device for refinery sludge carbonization treatment and carbon recovery
CN102482581B (en) Process for the production of bio-oil from solid urban waste
CN102557361B (en) Sludge gasification method
CN107117787B (en) Process method for synergistic pyrolysis of oily sludge by adding microalgae biomass
CN103627417A (en) Method for preparing biomass charcoal and jointly producing dimethyl ether from straw briquette
US20120160659A1 (en) Methodology for the removal of inorganic components from urban wastes, industrial wastes and sludges from sewage treatment plants
WO2009071541A2 (en) Process for making bio-oils and fresh water from aquatic biomass
WO2013051003A1 (en) A self-sustainable integrated solid and liquid waste management, treatment, and energy generation system and method
CN203411452U (en) Sludge carbonization and carbon recovery device for oil refinery
JP2009178657A (en) Subcritical water treatment method for organic sludge of oil refinery waste water
CN102719279B (en) Process for preparing gas by microwave carbon pyrolysis of municipal solid waste
US9650275B2 (en) Integrated process for the production of bio-oil from sludge coming from a wastewater purification plant
CN205347174U (en) Utilize plus sludge drying of living beings and processing apparatus that carbomorphism combined together
CN211394370U (en) System for pyrolysis of junked tire of boiler flue gas of thermal power plant
CN101875848A (en) Method for processing sludge pyrolytic oil
CN103846055A (en) Heat recovery method and system for recovering energy in water-rich biomass

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
TR01 Transfer of patent right

Effective date of registration: 20180103

Address after: 065001 Hebei city of Langfang province C New Austrian Science Park Economic Development Zone Xinyuan host city

Patentee after: Environmental Protection Technology Co., Ltd.

Address before: Langfang City, Hebei province Guangyang road 065001 North Zone

Patentee before: ENN SCIENCE & TECHNOLOGY DEVELOPMENT Co.,Ltd.