CN102557366A - Sludge treatment method and application thereof - Google Patents
Sludge treatment method and application thereof Download PDFInfo
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- CN102557366A CN102557366A CN2012100038828A CN201210003882A CN102557366A CN 102557366 A CN102557366 A CN 102557366A CN 2012100038828 A CN2012100038828 A CN 2012100038828A CN 201210003882 A CN201210003882 A CN 201210003882A CN 102557366 A CN102557366 A CN 102557366A
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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
Technical field
The present invention relates to a kind of method for sludge treatment and application thereof, in particular to comprise with mud under the condition of certain temperature and pressure, liquefy and prepare oil product method for sludge treatment, and this method in the application of sludge treatment.
Background technology
In recent years; The generation of China's municipal sludge continues to increase; According to " about the circular of construction fourth quarter in 2010 of national town sewage treatment facility and running condition "; By the end of the year 2010, China's town sewage treatment capacity reaches 343 billion cubic meters, and the sludge quantity that produces in the sewage treatment process also increases considerably.National mud turnout was about 2,199 ten thousand tons in 2010, produced 6.02 ten thousand tons in mud every day.According to present tempo, to 2015 end of the years, China's mud YO arrives 2,615 ten thousand tons to the major general, about 7.2 ten thousand tons of daily output mud.The minimizing of mud is handled and utilization rationally has been very serious problem.
Usually, water cut was about 80% through water cut after the drying and other treatment such as press filtration, and contains heavy metal (like Co, Pb, Ni etc.) up to 99% before municipal sludge was unprocessed.The meta-bolitess at different levels that contain amounts of protein, fat, MO, washing composition, soil ulmin, bacterium and bacterium in the organic composition of mud have wherein also comprised residue, waste oil lacquer, the remnants of various organic solvents, organic Jiao or the incomplete decomposing thing of parasite or ovum, mikrobe, some industrial macromolecular materials.
The general treatment process of mud is landfill and burning, has problems.For example, traditional sludge incineration processing scheme mostly is earlier mud to be collected and dehydrated to add a large amount of combustiblematerialss again after the processing and ignite, and puts into incinerator and burns.This burning mode is lower because of sludge calorific value on the one hand; And moisture content is big, causes fire box temperature low, and insufficient callable heat that burns is also few; So also higher usually fuel blending burning with calorific values such as coal, refinery cokes; Also have the inadequate solid residue of more burning after the burning, contain a large amount of oxysulfides, oxynitride and dioxin toxic and harmful in the middle of the tail gas simultaneously, atmosphere, HUMAN HEALTH are all produced detrimentally affect.
People had developed the method for sludge gasification afterwards, were H with organic matter transformation
2, CH
4, CO, CO
2Deng gas, further separation can get industrial chemicals.
In one Chinese patent application CN1405103A, a kind of treatment process of mud is disclosed, its technology that mainly adopts will be for will replace with wet oxidation at the chemical oxidation in traditional sludge treatment technique, and purpose is the organic matter in the mud is oxidized to CO
2, N
2Or oxynitride, dewatering is improved greatly, can also remove organic toxicity simultaneously.But do not realize organic effective utilization.
In one Chinese patent application CN101705105A, a kind of biomass liquefied oil and preparation method thereof is disclosed, its disclosure is with pyrolyzing sludge, obtains the method for biomass liquefied oil.This method mainly is to adopt high temperature with pyrolyzing sludge, obtain biomass liquefied oil therefrom; But what adopt in the method is normal pressure; Therefore the utilization ratio of the organic substance in the mud is extremely low; And operating process need be carried out in reducing atmosphere or inert atmosphere, has increased running cost and operation easier.In addition, the residence time of its technology is long, and the processing power of unit time is low.
Therefore, press at present a kind of with the organic substance in the mud change into oil product and effectively utilize more fully, the smaller method of energy consumption simultaneously.
Summary of the invention
In order to address the above problem, contriver of the present invention furthers investigate, and the result finds; Through under specific temperature and pressure, it being reacted in mud; Can the organic substance in the mud be prepared into oil product, the oil product yield is high, thereby has not only reduced the amount of mud; But also fully the organic substance in the mud is utilized fully again, realized the recycling of refuse.In addition; Advantage of the present invention is that also the reaction times is very short; And technological process does not need reducing atmosphere or inert atmosphere protection, the energy consumption of method of the present invention is smaller simultaneously, helps the application in industry, reached thus the application invent the purpose that will realize.
As everyone knows, states such as material can be solid-state, liquid, gaseous state and supercritical state exist, and the residing state of material depends on state parameters such as its temperature, pressure, density, composition.When the temperature and pressure of material is higher than its critical temperature and emergent pressure simultaneously, claim that then it is in supercritical state.Supercritical state is different from gaseous state and liquid state, and it has special physicochemical character.Supercritical water is a kind of of supercutical fluid.When temperature is higher than 374.1 ℃, when pressure is higher than 22.12MPa (pressure described herein is absolute pressure, down with), water is in supercritical state, and very big change has taken place its character.For example; Under the non-supercritical state; Basic metal or alkaline earth metal hydroxides or basic metal or alkaline earth metal carbonate have good solubility usually in water, but in the water near above-critical state and supercritical state, their solubleness will sharply reduce; So that can from its aqueous solution, separate out, the solubleness of salt in overcritical reduces greatly.In addition, the specific inductivity of water reduces under the supercritical state, and polarity weakens, and this makes it more approach organism, therefore organic matter is had good solvency action, and it also has excellent mass transfer ability simultaneously, is a kind of ideal reaction medium.
The present invention relates to a kind of method for sludge treatment, this method comprises: mud is carried out liquefaction reaction under the subcritical or supercritical state of water, obtain oil product thus.Subcritical or the supercritical state of said water is meant that temperature is that 330～480 ℃, pressure are 15～30MPa.Said mud as raw material does not receive special qualification, can be direct mud from factory, hospital or municipal administration etc., but preferably before reacting, it purified.For example at first will purify from the mud of factory, hospital or municipal administration etc., to remove inorganic substance wherein, the mud after will purifying then is used for liquefaction reaction.Purification can be adopted any known method, for example gravity settling desanding.The mud that preferably contains at least a element in iron, cobalt, nickel, the molybdenum.
In addition, for the mud that uses as raw material in the application's invention, wherein the content of water does not receive special qualification, but usually preferred water-content is 65～99wt%, can regulate the water-content of mud through the method for routine.
Under the specified conditions of above-mentioned temperature and pressure; Water in the mud is in subcritical or supercritical state; Other composition in the mud is had an effect; Make organic substance and inorganic substance in the mud etc. begin to take place the chemical reaction of pyrolysis, reformation, conversion etc., thereby change into the oil product and the solids of gas, liquid.In addition, in mud, itself contain under the situation of metallic element of iron, cobalt, nickel, molybdenum etc., these metallic elements or their compound also have certain katalysis, have further strengthened the liquefaction yield of mud under this condition thus.
In above-mentioned method, as stated, the organic substance in the mud is through decomposition and reformation under above-mentioned certain conditions, and major part changes into the liquid product with high added value, i.e. oil product.
In addition, in the aforesaid method, be component for example water, inorganic substance and organic substance in the sludge components as the raw material of mud liquefaction, do not receive special qualification, but the concentration of preferred said solid sludge is 1～35wt%.As required, also can before carrying out the mud liquefaction reaction, in mud, add other water or remove the concentration that the portion water in the mud is regulated mud.
In the above-mentioned mud liquefaction reaction, further preferred 380～450 ℃ of temperature of reaction are the yield of oil product to improve liquid product.Reaction times can confirm according to concrete practical situation, but the preferred liquefaction reaction time be 1～60 minute, further be preferably 5～15 minutes.
In the method for sludge treatment of the invention described above, wherein the resulting product in mud liquefaction back comprises oil product, solid residue, moisture and synthetic gas.Product obtains petroleum naphtha, petrol and diesel oil and oil fuel respectively by oil product after cooling, separating.Petroleum naphtha is generally the general term of a part of oil lighting end; The distillation boiling range is at 30～200 ℃, and in method of the present invention, mostly the chemical composition that the mud liquefaction process produces is hydrocarbons; Approaching with the clear cut of oil, so define light constituent wherein with petroleum naphtha.Same reason, boiling range is defined as petrol and diesel oil 200～370 ℃ component; Boiling point is defined as oil fuel in the component more than 370 ℃.The cool to room temperature that is cooled to described herein.Said separation can be common separation means, for example distillation cutting, rectified purified, purification etc.
In addition, in above-mentioned mud liquefaction reaction, can add catalyzer as required, further improve the yield that mud is converted into oil product thus.The metallic element of iron, cobalt, nickel or the molybdenum etc. that contain mostly in the middle of the above-mentioned mud itself or their compound under this state of arts, also have certain katalysis, have further strengthened the liquefaction yield of mud under this condition thus.
In addition, the invention still further relates to the application of adopting above-mentioned method for sludge treatment processing mud.
Effect of the present invention
According to the present invention, through mud is carried out liquefaction reaction under given conditions, obtain being rich in the oil product of various oil, this method not only can have been carried out minimizing processing and harmless treatment to mud, has also realized the recycling of mud refuse simultaneously.Supercritical water or subcritical water have improved mass transfer and rate of heat transfer widely owing to have special physicochemical character, and the mud raw material is under this condition, and speed of response is accelerated greatly, and helps generating liquid oil.
Description of drawings
Fig. 1 is the synoptic diagram of an embodiment of the present invention.
Embodiment
Below, the applicant is elaborated with reference to 1 pair of embodiment of the present invention of accompanying drawing.But the present invention is not limited to this mode.
At first, will purify, then it is joined in the reactive system from the primary sludge raw material of municipal administration, hospital or factory (for example chemical plant etc.).This reactive system can comprise reactor drum and interchanger or well heater; Mud carries out liquefaction reaction at reactive system, and the product that obtains after the reaction comprises gas, liquid and solid, gets into separation system then to separate; Through after the separation system, gas, liquid, solid are able to separate.Wherein gaseous combustible is burnt heat release, and gives reactive system, perhaps isolated H with the energy transport that discharges
2Be circulated back to liquefying reactor and participate in carrying out liquefaction reaction, H
2The synthetic gas that had produced in the time of both can being derived from liquefaction also can replenish in addition; Can be used as uses such as The building as obtaining solids after the above-mentioned separation.And the liquid that obtains can obtain chemical through further handling.
In the above-mentioned method for sludge treatment, mud liquefaction reaction concrete steps are as follows.At first liquefying reactor is heated, pressurizes, making temperature of reaction is 330-480 ℃, preferred 380-450 ℃, and reaction pressure is 15-30Mpa, and under such temperature and pressure condition, water is in subcritical or supercritical state.Under above-mentioned reaction conditions; Mud begins to take place chemical reactions such as pyrolysis, reformation, conversion; In mud, itself contain under the situation of metallic elements such as iron, cobalt, nickel, molybdenum; The compound of these elements or these elements also has certain katalysis, can further strengthen the liquefaction yield of mud thus.Controlling reaction time is 1～60 minute, preferred 5～15 minutes.Generation comprises oil product (this oil product is gaseous state under reaction conditions) in interior reaction product, and by-product synthetic gas and residue.Oil product joined carry out refrigerated separation in the refrigerating unit, obtain liquid oil product and gasiform synthetic gas.The liquid oil product that will obtain again separates, and for example distillation cuts suitable cut, finally obtains petroleum naphtha, petrol and diesel oil and oil fuel.Synthetic gas then can be used for other industrial use, for example is used to prepare piped gas, perhaps, can be from this synthetic gas recover hydrogen, and the hydrogen that reclaims turned back in the reactor drum use as raw material.Residue can be used as material of construction through further processing and uses.
Embodiment
Below come further explain the present invention through enumerating embodiment.But the present invention is not limited to these embodiment.Need to prove that at this mud among embodiment is the municipal sludge of Zhengzhou City, the analysis of its mud is as shown in table 1.Other geographic municipal sludges have similar composition.
The technical analysis of table 1 mud and ultimate analysis
Embodiment 1
Through the gravity settling desanding, after will purifying from the raw sludge of municipal mud, forming sludge concentration is the slurry of 15wt%.Then this slurry is joined in the reactor drum, reactor drum is controlled to be 350 ℃ of temperature, reaction pressure 17.0MPa made sludge reaction 10 minutes under this condition.
Above-mentioned reaction is taken out reactant after finishing from reactor drum, cooling; Distillation then, obtaining liquid product is oil product, adopts the Agilent gas chromatography mass spectrometer that this liquid product is measured; The result knows that in this product, the content of petroleum naphtha is 52wt%; The content of petrol and diesel oil is that the content of 28wt% and oil fuel is 20wt%, and all the other are various impurity.The reaction conditions of this embodiment and the result who obtains through said determination are shown in table 3 in the lump.
The boiling range of each product is as shown in table 2:
Table 2 product boiling range table
Embodiment 2～16
Carrying out embodiment 2～16 with embodiment 1 similar operation, except reaction conditions different.Reaction conditions that it is concrete and reaction result are shown in table 3.1-3.3.
Comparative example 1～3
With with embodiment 1 similar operation compare the example 1～3, except reaction conditions different.Reaction conditions that it is concrete and reaction result are shown in table 3.4.
Reaction conditions and the reaction result of table 3.1 embodiment 1-4
Annotate:
*The oil product yield is the mass percent that oil product accounts for the moisture-and-ash-free basis raw material;
*Product is distributed as the percentage ratio of each the ingredients constitute oil product gross weight in the oil product
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; Under the situation outside the application invents described 330～480 ℃ of temperature of reaction; For example in the comparative example 1 and 2, the temperature of its reaction is respectively 300 ℃ and 500 ℃, outside scope of the present invention; Can be clear that the yield of the oil product in this comparative example 1～2 very low (being respectively 2.5wt% and 5.7wt%) by above-mentioned table 3.4.And, even temperature in above-mentioned scope, if reaction pressure outside above-mentioned scope, for example comparative example 3; Its pressure that adopts is 35MPa, though total oil product yield is increased, for example compares with embodiment 13; The yield of oil product has only improved 1.7wt%, but therefore it need high-tension apparatus owing to adopt higher pressure condition; And energy consumption is obviously increased, and cost raises, and this is very disadvantageous for the utilization in the industry.
Claims (10)
1. one kind prepares the method for sludge treatment of oil product through mud is liquefied, and it may further comprise the steps:
Through mud is carried out liquefaction reaction under the subcritical or supercritical state of water, obtain oil product.
2. method for sludge treatment as claimed in claim 1, wherein, the subcritical or supercritical state of said water is meant that temperature is that 330～480 ℃, pressure are 15～30MPa.
3. according to claim 1 or claim 2 method for sludge treatment, wherein, said mud will be for purifying the mud that the back obtains from factory or municipal mud.
4. like each described method for sludge treatment of claim 1-3, wherein, contain at least a element in iron, cobalt, nickel, the molybdenum in the said mud.
5. like each described method for sludge treatment of claim 1～4, wherein, the water-content of said mud is 65～99wt%.
6. according to each described method for sludge treatment of claim 1～5, the temperature of wherein said liquefaction reaction is 380～450 ℃.
7. according to each described mud liquifying method of claim 1～6, wherein, the time of liquefaction reaction is 1～60 minute, is preferably 5～15 minutes.
8. according to each described method for sludge treatment of claim 1～7, wherein, said oil product comprises petroleum naphtha, petrol and diesel oil and oil fuel.
9. according to the described method for sludge treatment of claim 1～8, after said oil product cooling, separating, obtain petroleum naphtha, petrol and diesel oil and oil fuel respectively.
10. the described method for sludge treatment of claim 1～9 is in the application of handling mud.
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Cited By (9)
| 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 |
| CN103614168A (en) * | 2013-12-09 | 2014-03-05 | 华东理工大学 | Processing method for preparing liquid fuel by performing sludge liquefaction |
| CN104593116A (en) * | 2015-01-30 | 2015-05-06 | 湖南大学 | Method for preparing solid molded fuel from biomass liquefaction residues |
| CN104961310A (en) * | 2015-07-09 | 2015-10-07 | 周宗南 | Method and device for modifying organic sludge to prepare fuel oil |
| CN105036501A (en) * | 2015-08-05 | 2015-11-11 | 新奥科技发展有限公司 | Sludge degradation treatment method |
| CN106753461A (en) * | 2016-11-22 | 2017-05-31 | 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 |
| CN107746723A (en) * | 2017-11-06 | 2018-03-02 | 沈阳航空航天大学 | A kind of method that sludge liquefaction prepares bio-fuel |
| 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 |
| CN115286195A (en) * | 2022-08-17 | 2022-11-04 | 中国人民大学 | Environment-friendly reaction device for continuously treating excrement |
Citations (1)
| 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 |
-
2012
- 2012-01-09 CN CN201210003882.8A patent/CN102557366B/en active Active
Patent Citations (1)
| 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 |
Cited By (12)
| 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 |
| CN103614168A (en) * | 2013-12-09 | 2014-03-05 | 华东理工大学 | Processing method for preparing liquid fuel by performing sludge liquefaction |
| 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 |
| CN104593116A (en) * | 2015-01-30 | 2015-05-06 | 湖南大学 | Method for preparing solid molded fuel from biomass liquefaction residues |
| CN104961310A (en) * | 2015-07-09 | 2015-10-07 | 周宗南 | Method and device for modifying organic sludge to prepare fuel oil |
| CN105036501A (en) * | 2015-08-05 | 2015-11-11 | 新奥科技发展有限公司 | Sludge degradation treatment method |
| CN106753461A (en) * | 2016-11-22 | 2017-05-31 | 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 |
| 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 |
| CN107746723A (en) * | 2017-11-06 | 2018-03-02 | 沈阳航空航天大学 | A kind of method that sludge liquefaction prepares bio-fuel |
| 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 |
| CN115286195A (en) * | 2022-08-17 | 2022-11-04 | 中国人民大学 | Environment-friendly reaction device for continuously treating excrement |
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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. |