CN107601804A - A kind of method that self-heating moulding oily sludge pyrolysis prepares adsorbent - Google Patents
A kind of method that self-heating moulding oily sludge pyrolysis prepares adsorbent Download PDFInfo
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- CN107601804A CN107601804A CN201710817060.6A CN201710817060A CN107601804A CN 107601804 A CN107601804 A CN 107601804A CN 201710817060 A CN201710817060 A CN 201710817060A CN 107601804 A CN107601804 A CN 107601804A
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- adsorbent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/40—Valorisation of by-products of wastewater, sewage or sludge processing
Abstract
The invention provides a kind of method that self-heating moulding oily sludge pyrolysis prepares adsorbent, this method includes：Aqueous oily sludge is mixed with destructive distillation residue, is molded, then carries out carbonization, the solid product completed after destructive distillation is adsorbent.Wherein, water contained oil sludge is mixed moisture control below 50% with destructive distillation residue, oil content is 6~10%, mix adhesive special simultaneously, enter roller briquetting machine after stirring to be molded, dry and moisture content is down to less than 4%, be re-fed into gas retort and be heated to 500~600 DEG C, caused fuel gas, which is returned to burn into gas retort, in retort process provides destructive distillation thermal source；Complete the product after destructive distillation to cool down with air heat-exchange, the material oil content after cooling is reduced to less than 0.3%, can be used as water process adsorbent, and adsorbance is up to more than the 70% of commercially available wooden adsorbent adsorbance；Hot-air is admitted to heating furnace and burnt with caused oil gas in retort process；Greasy filth prepares adsorbent and realizes recycling and innoxious.
Description
Technical field
The present invention is on a kind of oil-containing fixed-end forces and application technology as the second resource, is on a kind of self-heating specifically
The method that moulding oily sludge pyrolysis prepares adsorbent, and thus obtained adsorbent and its application.
Background technology
Pyrolysis is solid waste harmless treatment, the common technology of recycling, is widely used in house refuse, medical waste
Deng treatment of wastes produced, and it is gradually available for the processing of oily sludge.The reduction of oily sludge pyrolysis processing can reach
More than 50%, organic compound can be stablized, and caused liquid pyrolysis oil may be used as fuel and derivative chemical products etc..
In addition, the process of oily sludge is handled using pyrolysis way, the heavy metal accumulation in oily sludge can also be pyrolyzed
In residue, and form of the heavy metal in pyrolysis residue is than having higher resistant to leaching in bottom ash after burning.It is residual after pyrolysis
Slag may be used as pollutant sorbing material, or pyrolytic process provides energy and supported.
CN102874997A discloses a kind of oily sludge pyrolysis and its method of resource, wherein being into oily sludge
Add colliery powder and Fe3O4Afterwards, mixture mixed successively, be granulated, preheating and drying (using pyrolysis gas as thermal source) and heat
Solution, then the pyrolysis gas discharged with recirculated water to pre-dryer cool down, and the steam and hydro carbons in pyrolysis gas are respectively with containing greasy dirt
Water and liquid hydrocarbon form condense out, and oil-polluted water enters sewage farm and does processing up to standard, and liquid hydrocarbon recycles, and body refuse is through work
Rich magnetic carbonaceous adsorbent is made after change.
CN103553040A discloses a kind of oily sludge pyrolysis processing, wherein being hot altogether with oily sludge using petroleum coke
Solution prepares porous carbon, including step：(1) oily sludge is carried out predrying；(2) oily sludge of gained is mixed with petroleum coke
Uniformly；(3) oily sludge of well mixed gained and petroleum coke mixtures crushed, ground, screening；(4) by gained mixture
Material is impregnated in compound activator solution, is dried after dipping；(5) obtained mixture is placed in pre-activate in low-temp reaction stove；
(6) product of gained is placed in high temperature reaction stove and continues to activate, cool to normal temperature with the furnace；(7) gained activation products are added
Washed to obtain solid product using distilled water after soaking in hydrochloric acid or sulfuric acid solution, solid product is dried to obtain porous carbon
Material.
It is carbon containing using greasy filth and other height that above-mentioned greasy filth pyrolysis, which prepares porous carbon materials or the invention of carbonaceous adsorbent,
Simultaneously prepared by activated processing for material copyrolysis, and relative cost is higher or complex process.This research is dry with itself using greasy filth
It is quenched to evaporate product mixing, is not required to introduce external source carbon material, residue yield is few, and technique is relatively easy, processing cost is low, through moulding
The generation of flying dust can be greatly decreased after processing, oil quality is good, and fume treatment difficulty reduces；The deep fat gas reuse reclaimed in processing
Can partially or completely solve the demand of pyrolyzing heat.
The content of the invention
It is an object of the present invention to develop a kind of improved oil-containing fixed-end forces and recycling new technology, solve
The problems such as thermic load present in existing oily sludge pyrolytic process is high, oil quality is poor, residue also needs harmless treatment, realize
The minimizing of greasy filth, recycling and innoxious.
On the one hand, the invention provides a kind of oily sludge pyrolysis treating method, this method to include：
Aqueous oily sludge is mixed with its destructive distillation residue, is molded, then carries out carbonization.Complete consolidating after destructive distillation
Body product can be used as adsorbent, and its adsorbance is close to traditional wood activated charcoal.That is, oily sludge pyrolysis processing of the invention
Method, it is a kind of method that oily sludge pyrolysis processing prepares adsorbent.
According to specific embodiments of the present invention, oily sludge pyrolysis treating method of the invention, the destructive distillation residue contains
Oil cut rate is less than 0.3%, and moisture content is less than 10%.Specifically, described destructive distillation residue can be that the dry distillation of oil mud of traditional handicraft is residual
Slag or the solid residue (i.e. described adsorbent) prepared from greasy filth of the present invention pyrolysis.
According to specific embodiments of the present invention, oily sludge pyrolysis treating method of the invention, aqueous oily sludge
In the mixed system mixed with destructive distillation residue, moisture content≤50%, oil content 6~10% are controlled.
According to specific embodiments of the present invention, oily sludge pyrolysis treating method of the invention, aqueous oily sludge
In the mixed system mixed with destructive distillation residue, binding agent is also mixed with.Specifically, the main component of the binding agent is humic acid
Sodium, it is according to 5~15 by humic acid, sodium hydroxide and water：0.5~2：What 50~200 ratio was mixed with, dosage
For the 0.5%-2.0% of oily sludge amount.
According to specific embodiments of the present invention, oily sludge pyrolysis treating method of the invention, it was pyrolyzed to reduce
Dust in journey, avoids pipeline blockage, and the mixture that aqueous oily sludge is mixed with destructive distillation residue first is sent into shaping system
System shaping, prepares particle diameter in 10~50mm, and intensity and is dried to moisture content below 4%, then carry out in more than 30N particle
Destructive distillation.
According to specific embodiments of the present invention, in oily sludge pyrolysis treating method of the invention, the bar of carbonization
Part is：500-600 DEG C, 2~4h is pyrolyzed, seals anaerobic.
According to specific embodiments of the present invention, in oily sludge pyrolysis treating method of the invention, by retort process
Caused fuel gas, which is used to burn, provides destructive distillation thermal source.
According to specific embodiments of the present invention, in oily sludge pyrolysis treating method of the invention, after completing destructive distillation
Solid product cools down with air heat-exchange, and hot-air is sent into heating furnace and burnt with caused oil gas in retort process.
Pyrolysis residue of the invention by the use of itself is quenched, the petroleum resources of itself no longer needs extra fuel to realize as fuel
It is pyrolyzed and prepares adsorbent, adsorbance exceedes wood activated charcoal.
The present invention method, can directly handle more homogeneous oily sludge include tank bottom mud, bottom of pond mud, the mud of refinery three,
Oil-base mud and chemical engineering sludge etc., it can also be used to by sorting pretreatment, the ground sludge of centrifuging treatment and mixing greasy filth
Deng.
On the other hand, present invention also offers a kind of adsorbent, it includes being pyrolyzed according to oily sludge of the present invention
The solid product completed after destructive distillation that processing method obtains.Preferably, the adsorbent oil content is below 0.3%, specific surface area
Reach 400-500m2/g。
On the other hand, the application present invention also offers described adsorbent in as water process adsorbent.More
Body, the adsorbent can be used for Adsorption oily waste water COD, petroleum substance, its absorption property is up to commercially available wood
More than the 70% of matter adsorbent adsorbance.
In summary, the invention provides a kind of self-heating moulding oily sludge pyrolysis to prepare adsorbent technique, wherein will contain
(within 50%, oil content controls within the 10% moisture control) mixing according to a certain percentage of water greasy filth and destructive distillation residue,
Shaping, pyrolysis can handle the aqueous larger greasy filth that conventional equipment can not be handled.The technique need not be carried out to oily sludge
Dehydration pretreatment, as long as water contained oil sludge and destructive distillation residue are mixed according to a certain percentage, be molded, are pyrolyzed, significantly reduces
Pretreatment cost, and by the way that the aqueous larger greasy filth that conventional equipment can not handle can be handled with powder forming technique.It is logical
Cross adjustment pyrolysis parameters of rock (by the way that the pyrolysis temperature of greasy filth, extension or the mode such as pyrolysis time for shortening greasy filth is raised and lowered) simultaneously
Activation is played by means of caused steam in greasy filth pyrolytic process, obtains the greasy filth residue with large specific surface area, can
Used as adsorbent.Caused waste water is directly entered burner combustion with waste gas in pyrolytic process, and is discharged into flue gas
Air, emit no waste water in whole production process.The technique is effectively by the use of caused lighter hydrocarbons after oil destructive distillation as thermal source, no
External heat source is needed, reduces the wasting of resources, it is cost-effective.The present invention technology, can realize oily sludge harmless treatment and
Recycling；Realize that the three wastes of discharge are up to standard；Adsorbent adsorbance prepared by greasy filth reaches wood activated charcoal adsorbance
More than 70%, it is also used as the filtrate in water-treatment biological filter tank.
Brief description of the drawings
Fig. 1 is the schematic flow sheet that the self-heating moulding oily sludge pyrolysis of the present invention prepares the method for adsorbent.
Embodiment
The present invention will be further described with reference to embodiments, and these embodiments are not intended to limit the invention.
It is shown in Figure 1, should the invention provides a kind of method that self-heating moulding oily sludge pyrolysis prepares adsorbent
Method mixes according to a certain percentage including water contained oil sludge with destructive distillation residue, control moisture content≤50%, oil content 6~10%, together
When mix adhesive special, roller briquetting machine is entered after stirring and is molded, shaped article is using heat smoke drying to moisture content
≤ 4%, it is heated to 500~600 DEG C or so (can adjust temperature according to actual conditions) subsequently into gas retort, is produced in retort process
Raw fuel gas foldback enters heating furnace burning and provides destructive distillation thermal source；Complete the product after destructive distillation to cool down with air heat-exchange, cooling
Material oil content afterwards is reduced to less than 0.3%；Hot-air is admitted to heating furnace and burnt with caused oil gas in retort process.It is dry
The dust concentration after bag-type dust of waste gas caused by dry section is less than 30mg/m3；According to the test to sulphur in greasy filth and residue, flue gas
Middle SO2Content is in 100mg/m3Within, the technique greasy filth reclaimed water point and pyrolysis water are discharged into air with flue gas, entirely produce
Emitted no waste water in journey.The technique effectively by the use of caused lighter hydrocarbons after oil destructive distillation as thermal source, is not required to extra fuel, reduced
The wasting of resources, it is cost-effective, and bioxin will not be produced.
Embodiment 1
Adsorbent, greasy filth physico-chemical property such as table are prepared using scum bottom sludge caused by the condensed oil sewage treatment plant of Liaohe Oil Field
1：
The scum bottom sludge index of correlation of table 1
| Moisture content, % | Oil content, % | Solid content, % |
| 62.70 | 8.41 | 28.89 |
The weight proportion of scum bottom sludge and pyrolysis residue is 3：1, and 1.5% binding agent is added, after mixing is quenched, enter
Roller briquetting machine is molded, balling-up intensity 35N/, and then shaped article enters the drying of indirect-heating rotary furnace and pyrolysis, pyrolysis temperature
550 DEG C, pyrolysis time 3h, you can obtain adsorbent product.
Adsorbent index such as table 2 prepared by scum bottom sludge：
Adsorbent index of correlation prepared by the scum bottom sludge of table 2
Under equal experiment condition, adsorbent prepared by scum bottom sludge is commercially available to oily waste water COD, petroleum-type removal ability
The 120% of wooden adsorbent.
Embodiment 2
Adsorbent, greasy filth physico-chemical property such as table 3 are prepared using heavy oil greasy filth caused by the oil field of Xinjiang：
The heavy oil greasy filth index of correlation of table 3
| Moisture content, % | Oil content, % | Solid content, % |
| 57.97 | 12.04 | 29.99 |
The weight proportion of heavy oil greasy filth and pyrolysis residue is 4：1, and 1.0% binding agent is added, after mixing is quenched, enter
Roller briquetting machine is molded, balling-up intensity 41N/, and then shaped article enters the drying of indirect-heating rotary furnace and pyrolysis, pyrolysis temperature
600 DEG C, pyrolysis time 3h, finally give adsorbent product.
Adsorbent index such as table 4 prepared by heavy oil greasy filth：
Adsorbent index of correlation prepared by the heavy oil greasy filth of table 4
Under equal experiment condition, adsorbent prepared by heavy oil greasy filth can reach to oily waste water COD, petroleum-type removal ability
The 90% of commercially available wooden adsorbent.
Embodiment 3
Using the clay standby adsorbent of Xinjiang oil field oil product storage tank tank bottom, greasy filth physico-chemical property such as table 5：
The tank bottom mud index of correlation of table 5
| Moisture content, % | Oil content, % | Solid content, % |
| 25.12 | 43.06 | 31.82 |
The weight proportion of clear tank greasy filth and pyrolysis residue is 1：4, and 1.0% binding agent is added, after mixing is quenched, enter
Roller briquetting machine is molded, balling-up intensity 32N/, and then shaped article enters the drying of indirect-heating rotary furnace and pyrolysis, pyrolysis temperature
550 DEG C, pyrolysis time 3h, finally give adsorbent product.
Adsorbent index such as table 6 prepared by tank bottom oil sludge：
Adsorbent index of correlation prepared by the tank bottom oil sludge of table 6
Under equal experiment condition, adsorbent prepared by tank bottom oil sludge can reach to oily waste water COD, petroleum-type removal ability
The 75% of commercially available wooden adsorbent.
Embodiment 4
Adsorbent, greasy filth physico-chemical property such as table 7 are prepared using the greasy filth in Liaohe River oil field cleaning well site：
Table 7 is cleared out a gathering place greasy filth index of correlation
| Moisture content, % | Oil content, % | Solid content, % |
| 5.85 | 5.25 | 88.90 |
The greasy filth that will clear out a gathering place is crushed, and is stirred with 1.5% binding agent, is molded into roller briquetting machine, balling-up
Intensity 43N/ is individual, and then shaped article enters the drying of indirect-heating rotary furnace and is pyrolyzed, 550 DEG C, pyrolysis time 3h of pyrolysis temperature, most
Adsorbent product is obtained eventually.
Adsorbent index such as table 8 prepared by greasy filth of clearing out a gathering place：
Table 8 clear out a gathering place greasy filth preparation adsorbent index of correlation
Under equal experiment condition, adsorbent prepared by greasy filth of clearing out a gathering place can reach to oily waste water COD, petroleum-type removal ability
The 80% of commercially available wooden adsorbent.
Embodiment 5
Adsorbent, greasy filth physico-chemical property such as table 9 are prepared using caused tank bottom oil sludge during Shengli Oil Field secondary oil recovery：
The tank bottom oil sludge index of correlation of table 9
| Moisture content, % | Oil content, % | Solid content, % |
| 76.30 | 18.00 | 5.70 |
The weight proportion of tank bottom oil sludge and pyrolysis residue is 2：1, content of binder 1.5%, after mixing is quenched, enter
Roller briquetting machine is molded, balling-up intensity 38N/, and then shaped article enters the drying of indirect-heating rotary furnace and pyrolysis, pyrolysis temperature
600 DEG C, pyrolysis time 3h, finally give adsorbent product.
Adsorbent index such as table 10 prepared by tank bottom oil sludge：
Adsorbent index of correlation prepared by the tank bottom oil sludge of table 10
Under equal experiment condition, adsorbent prepared by tank bottom oil sludge can reach to oily waste water COD, petroleum-type removal ability
The 90% of commercially available wooden adsorbent.
The present invention is only illustrated with the above-mentioned example that is embodied as, the structure and size of each part, pressure-resistant, set location and its company
Connecing to be varied from.On the basis of technical solution of the present invention, all inventive principles according to the present invention are entered to individual part
Capable improvement or equivalents, it should not exclude outside protection scope of the present invention.
Claims (11)
1. a kind of method that oily sludge pyrolysis prepares adsorbent, this method include：
Aqueous oily sludge is mixed with destructive distillation residue, the mixed system for controlling aqueous oily sludge to be mixed with destructive distillation residue
In, moisture content≤50%, oil content 6~10%；
The mixed system that aqueous oily sludge is mixed with destructive distillation residue is sent into roller briquetting machine shaping, and dries to moisture content
Less than 4%；
Dried material carries out carbonization, and the solid product completed after destructive distillation is adsorbent.
2. according to the method for claim 1, wherein, the destructive distillation residue oil content is less than 0.3%, and moisture content is less than
10%.
3. the method according to claim 11, wherein, in the mixed system that aqueous oily sludge mixes with destructive distillation residue,
Also it is mixed with binding agent.
4. according to the method for claim 3, wherein, the main component of the binding agent is sodium humate, it is planted by corruption
Acid, sodium hydroxide and water are according to 10：1：What 100 ratio was mixed with, dosage is the 0.5%-2.0% of greasy filth weight.
5. according to the method for claim 1, wherein, the oily sludge includes tank bottom mud, bottom of pond mud, the mud of refinery three, oil
Base mud or chemical engineering sludge, or including by sorting pretreatment, the ground sludge mud of centrifuging treatment or mixing greasy filth
Deng.
6. according to the method for claim 1, wherein, the condition of carbonization is：500~600 DEG C.
7. according to the method for claim 1, wherein, provide caused fuel gas in retort process to destructive distillation for burning
Thermal source.
8. according to the method for claim 1, wherein, complete the solid product after destructive distillation and cooled down with air heat-exchange, hot-air
Heating furnace is sent into burn with caused oil gas in retort process.
9. a kind of adsorbent, it includes the solid completed after destructive distillation obtained according to the method described in any one of claim 1~8
Product.
10. adsorbent according to claim 9, for the adsorbent oil content below 0.3%, specific surface area reaches 400-
500m2/g。
11. the adsorbent described in claim 9 or 10 is as water process adsorbent；Preferably, wherein being by the adsorbent
For pollutants such as surfactant, petroleum-types in Adsorption oily waste water.
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| CN108913175A (en) * | 2018-06-21 | 2018-11-30 | 中国矿业大学 | A kind of combined cycle system and its application method based on abandoned biomass catalytic pyrolysis product processing organic wastewater |
| CN110540858A (en) * | 2019-09-11 | 2019-12-06 | 山西领君重工机械设备有限公司 | Oil sludge recovery treatment method |
| CN111233301A (en) * | 2020-03-06 | 2020-06-05 | 山东产研绿洲环境产业技术研究院有限公司 | Oil sludge treatment method and oil sludge treatment system |
| CN111621316A (en) * | 2020-05-29 | 2020-09-04 | 浙江华环环境有限公司 | Additive for recycling common industrial garbage and processing method |
| CN112479529A (en) * | 2020-12-04 | 2021-03-12 | 湖北爱国环保技术开发有限公司 | Process for treating oil sludge by dry distillation method |
| CN114671589A (en) * | 2022-03-17 | 2022-06-28 | 中国科学院城市环境研究所 | Method for synergistic harmless recycling treatment of oil sludge and fly ash |
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| CN114671589A (en) * | 2022-03-17 | 2022-06-28 | 中国科学院城市环境研究所 | Method for synergistic harmless recycling treatment of oil sludge and fly ash |
| CN114671589B (en) * | 2022-03-17 | 2023-09-29 | 中国科学院城市环境研究所 | Method for synergistic harmless recycling treatment of oil sludge and fly ash |
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