CN1109654C - Process for using petro-chemical mud to prepare adsorbent used to recover oil on water surface - Google Patents
Process for using petro-chemical mud to prepare adsorbent used to recover oil on water surface Download PDFInfo
- Publication number
- CN1109654C CN1109654C CN 97112251 CN97112251A CN1109654C CN 1109654 C CN1109654 C CN 1109654C CN 97112251 CN97112251 CN 97112251 CN 97112251 A CN97112251 A CN 97112251A CN 1109654 C CN1109654 C CN 1109654C
- Authority
- CN
- China
- Prior art keywords
- adsorbent
- sorbent material
- oil
- water surface
- mud
- 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.)
- Expired - Fee Related
Links
Abstract
The present invention relates to a method for preparing adsorbent for recovering oil on water surfaces by petrochemical sludge, which belongs to the technical field of environmental protection. The present invention is characterized in that the present invention is a novel technique by which charring as well as activation are carried out by water in sludge at the charring temperature of 300 DEG C to 350 DEG C. Prepared adsorbent has lipophilic and hydrophobic performance, and can be suspended on water surfaces for a long term. The suspension rate is 100%. The adsorbent has developed macropores, 1 gram of adsorbent can absorb 14.2 grams of crude oil, and the removal rate is higher than 99.6%. The adsorbent which is prepared according to American Standard of Testing Materials (ASTM) belongs to the best class for recovering spill oil on the water surfaces.
Description
The present invention relates to a kind of processing method of utilizing the petrochemical sludge preparation to remove oil adsorbent, belong to environment protection
Technical field.
Petrochemical wastewater mud must be handled and be disposed owing to the hazardness to environment.
The approach of sewage sludge harmlessness is had: burn and landfill.Burn and landfill just makes the approach of sewage sludge harmlessness, do not obtain the product that is worth, and processing costs is quite high.
The approach of recycling sludge is had: fertile as farming, produce biogas, make material of construction.
Fertile as farming, producing biogas, is to make mud obtain the approach of resource utilization though make material of construction, and the secondary pollution that mud causes is not still eliminated, to waters on every side, underground water and soil work the mischief the organic constituent that contains as mud through weathering, evaporation and infiltration meeting; The microbial bacterial that contains in the mud just can kill when must be heated to greater than 80 ℃ in addition.And aforesaid method can't reach.
The CN86101176A patent disclosure a kind of method of utilizing similar feedstock production sorbent material, its method is to put into together in the closed reactor that covers one-way exhaust valve with mud with by the auxiliary agent that materials such as phosphoric acid are formed, place and carry out the anaerobic thermal degradation in the pre-heated Reaktionsofen, temperature is controlled between 600 ℃～1000 ℃, and reaction finishes back cooling fast.This product can be made products such as sorbent material, carbon black through technologies such as fragmentation, activation.The shortcoming of this method is: 1. temperature of reaction height, i.e. energy consumption height; 2. add the auxiliary agent that material such as phosphoric acid is formed in the preparation process, increased production cost; 3. technical process is long, carry out the anaerobic thermal degradation in the Reaktionsofen after, also to further activate; 4. the performance of Zhi Bei sorbent material and Application Areas are not illustrated.
The petrochemical sludge that utilizes that is proposed in some bibliographical informations prepares gac both at home and abroad, and complicated process of preparation adopt charing and activation two step process, and temperature is higher, and product mainly is made up of activated carbon composition; Gac is owing to the microvoid and the transitional pore that mainly contain prosperity, and suspension is poor, is not suitable for planar water surface oil spilling.
Purpose of the present invention is to provide a kind of petrochemical sludge that utilizes to prepare new processing method and product that sorbent material is used for recycle-water surface oil spilling.The novel process that adopts charing and activation to unite two into one, carbonization temperature is lower.With the sorbent material that this method makes, it is formed except activated carbon composition, also contains a considerable amount of organism, and contains flourishing macropore, has the suspensibility of good lipophilic-hydrophobic property and 100%.
The objective of the invention is to be achieved through the following technical solutions: mud is heated rapidly to 300～350 ℃ with the speed greater than 25 ℃/minute in the charing process furnace, charing was taken out after 2 hours, promptly obtains sorbent material after cooling, fragmentation, screening and the packing.
Carbonization temperature is 300～350 ℃, and waste gas circulation is used and to be meant recycling of not condensable gases that carbonization process produces, reducing the off gas treatment cost, and recyclable heat energy.The granularity of sorbent material fragmentation is less than 1 millimeter, packs the circular felt shape of sorbent material with mesh size 50～150 orders, thickness＜3 millimeter, 1～10 meter of diameter.Prepared sorbent material is contained-CH by gac
3,=CH
2, ≡ CH group organism and contain Al
2O
3, CaO, SiO
2, Fe
2O
3Inorganics form, the weight percent of each component is: gac 21.1%, organism 48.7%, inorganics 30.2%, proportion 0.56～0.69, suspensibility are 100%.
The characteristic of utilizing oil viscosity to raise and reduce with temperature, saturated sorbent material is heated to 501～05 ℃, can make sorbent material obtain regeneration, and oil can obtain reclaiming simultaneously.
Characteristics of the present invention are to utilize original moisture in the mud, owing to the distillation and the activation of water vapor, have increased the pore structure of sorbent material in the charing heat-processed, the novel process that promptly adopts charing and activation to unite two into one.This technology has following characteristics: 1. temperature of reaction is low, and promptly energy consumption is low; 2. preparation process does not add any auxiliary agent, reduces production cost; 3. technical process is short, the novel process that adopts charing and activation to unite two into one.
Characteristics of the present invention are that the sorbent material of preparation has lipophilic-hydrophobic property, can be suspended in water surface for a long time, can reach more than one month, suspensibility is the adsorbable 14.2 gram crude oil of 100%, 1 gram sorbent material, clearance＞99.6%, the oil that is adsorbed can obtain reclaiming, sorbent material reproducible utilization, recycling number of times＞5 time, according to American society standard (ASTM), the sorbent material of preparation belongs to the best class of recycle-water surface oil spilling.
American society standard (ASTM)
| Specific absorption | The sorbent material classification |
| ＞10∶1 5∶11～0∶1 ＜5∶1 | Preferably better general |
The sorbent material that is used for planar water surface oil spilling at present has:
Organic adsorbent---comprise straw, peat, sawdust, wood chip, corn stalk, feather, asbestos, wool and other material containing carbon, these materials exist in a large number at occurring in nature.The specific absorption of most of organic adsorbent is synthesized a kind of efficient oil absorption material collagen protein foam abroad recently at 1～10g oil/1g sorbent material.Most of organic adsorbent is an oleophilic drainage, can be powdery, granular, loose shape or other packing material.
Inorganic adsorbent---generally be some mineral substance, as perlite, vermiculite, glass fibre, volcanics, specific absorption 1～8g oil/1g the sorbent material of inorganic adsorbent, its specific absorption is less than 2g oil/1g sorbent material in many cases, the shortcoming of inorganic adsorbent is except that specific absorption is little, because it is than great, and possess hydrophilic property, be easy to sink to the bottom, though this has eliminated water surface oil pollution, but do not reduce total oil pollution to the infringement that environment causes, endanger benthic growth, and the oil that is adsorbed also can not get recycling.Because these Powdered inorganic adsorbents require operator to be with breathing mask to the hazardness of respiratory system.The advantage of inorganic adsorbent is that the source is abundant, low price.
Synthetic adsorbent---comprise artificial polymeric material, as Polyurethane, polyethylene, polypropylene, nylon fiber, urea (first) urea formaldehyde foam, synthetic adsorbent is that the ideal sorbing material is used for planar water surface petroleum-type pollutent, and shortcoming is to involve great expense.
One aspect of the present invention makes harmful recycling sludge, Zhi Bei sorbent material is in all kinds of sorbent material products level preferably simultaneously, and use this sorbent material to environment non-secondary pollution (by to adsorbing the monitoring of back water), owing to adopt 300～350 ℃ of carbonization temperatures, the bacterium that exists in the mud all can be killed, therefore, this sorbent material meets the requirement of engine hygiene simultaneously.
It is composed as follows that embodiment 1. preparation sorbent materials prepare the used petrochemical plant mud of sorbent material:
| The No sample | Moisture (%) | Organism (accounting for butt) (%) | Inorganics (accounting for butt) (%) | Fixed carbon (accounting for butt) (%) | The water solubles in the ash content (%) | Proportion (20oC) |
| 12345 is average | 82.1 81.6 81.2 83.4 85.4 82.3 | 72.1 73.0 72.0 71.3 63.9 70.6 | 18.2 18.6 18.8 18.5 28.6 19.2 | 9.7 8.4 9.2 10.2 7.5 10.2 | -- -- -- -- -- 18.7 | -- -- -- -- -- 0.50 |
When the charing furnace temp is raised to 300～350 ℃, put into 60 gram average samples, after 2 hours, take out sample from the charing process furnace, in air, cool off earlier, weigh after in moisture eliminator, being cooled to room temperature then.The sorbent material of preparation grinds in mortar, and screening is divided into the component less than the 1mm granularity, the saturated sorbent material of absorption is easier to be separated from the water surface in order to make, the circle of making 4 centimetres of diameters with 50～150 purpose screen clothes approaches bag, and granularity is less than 1 millimeter, and 200 milligrams of sorbent materials evenly are layered in the sack.2. planar water surface crude oil test
In 100 ml beakers (5 centimetres of internal diameters), add 60 ml distilled waters, splash into 3.2 gram crude oil, crude oil is diffused in water surface gradually and forms circular oil film, thickness 1.73mm, 20 ℃ of room temperatures, soak time was tested in 1 hour with the sorbent material of packing of above-mentioned preparation, and adsorption rate is 14.2 gram crude oil/gram sorbent materials, the water surface surplus oil adopts secondary absorption, and clearance is 99.6%.
The weight percent composition and the proportion that prepare the sorbent material that is used for recycle-water surface oil spilling under the top condition of laboratory are as follows:
3. reclaim the oil that is adsorbed, reproducing adsorbent.
| Sorbent material granularity (mm) | Sorbent material is formed | |||
| Proportion | Inorganics (%) | Organism (%) | Activated carbon composition (%) | |
| ＜0.5 0.5～1.0 | 0.69 0.56 | 29.8 31.2 | 54.8 40.9 | 17.4 29.9 |
Be under 50～105 ℃ the condition, above-mentioned saturated sorbent material to be carried out oil recovery in regeneration temperature, reproducing adsorbent simultaneously after the oil film behind the absorption 1.73mm is saturated, carries out 5 refiltered oils and reproducing adsorbent.The results are shown in following table:
Refiltered oil and reproducing adsorbent result
| Recovered frequency | Adsorption rate (g/g) | The rate of recovery (%) | Residual rate (g/g) |
| 1 2 3 4 5 | 11.6 5.9 4.4 3.7 3.4 | 65.2 60.0 52.7 48.3 46.5 | 4.1 4.0 4.0 3.9 4.0 |
Spent sorbents after repeatedly reclaiming can prepare sorbent material again by the thermolysis charing, or acts as a fuel, and its thermal value is 6700～7800 kilocalories/kilogram.
Claims (1)
1, a kind of processing method of utilizing petrochemical sludge to prepare sorbent material, it is characterized in that: according to following preparation process, be that mud is heated to 300～350 ℃ with the rapid heating speed greater than 25 ℃/minute in the charing process furnace, charing was taken out after 2 hours, obtain sorbent material after cooling, fragmentation, screening and the packing, prepared sorbent material is contained-CH by gac
3,=CH
2, ≡ CH group organism and contain Al
2O
3, CaO, SiO
2, Fe
2O
3Inorganics form, the weight percent of each component is: gac 21.1%, above-mentioned containing-CH
3,=CH
2, ≡ CH group organism 48.7%, the above-mentioned Al that contains
2O
3, CaO, SiO
2, Fe
2O
3Inorganics 30.2%, proportion 0.56～0.69, suspensibility are 100%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97112251 CN1109654C (en) | 1997-07-15 | 1997-07-15 | Process for using petro-chemical mud to prepare adsorbent used to recover oil on water surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97112251 CN1109654C (en) | 1997-07-15 | 1997-07-15 | Process for using petro-chemical mud to prepare adsorbent used to recover oil on water surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1171370A CN1171370A (en) | 1998-01-28 |
| CN1109654C true CN1109654C (en) | 2003-05-28 |
Family
ID=5172163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97112251 Expired - Fee Related CN1109654C (en) | 1997-07-15 | 1997-07-15 | Process for using petro-chemical mud to prepare adsorbent used to recover oil on water surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1109654C (en) |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1326782C (en) * | 2005-05-12 | 2007-07-18 | 哈尔滨工业大学 | Application of filtration-adsorption material made of sludge in reuse water treatment |
| CN101559354B (en) * | 2009-04-29 | 2010-12-01 | 同济大学 | Preparation method of sludge absorber and applications thereof |
| CN101747900B (en) * | 2009-12-14 | 2012-07-04 | 昆明理工大学 | Method for preparing soil conditioner by carrying out carbonization treatment on lake substrate sludge |
| CN101885372A (en) * | 2010-07-03 | 2010-11-17 | 燕山大学 | High-efficiency oil spilling cleaning boat at sea |
| CN102294217B (en) * | 2011-06-23 | 2012-10-17 | 中国石油天然气集团公司 | Method for preparing new oil-extraction wastewater adsorbent by using pyrolysis residues of oil sludge |
| CN102328967B (en) * | 2011-09-30 | 2013-01-02 | 北京师范大学 | Biodegradable floating bed with function of adsorbing sea water polluted by oil spillage |
| CN102432144B (en) * | 2011-11-01 | 2013-04-17 | 华南再生资源（中山）有限公司 | Method for preparing microporous adsorbent from sludge, product and special equipment |
| CN104888716A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Adsorbent capable of removing toxic substances in exhaust gas |
| CN104888688A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Adsorbent capable of absorbing soil heavy metal |
| CN104923178A (en) * | 2015-05-21 | 2015-09-23 | 安徽凤凰滤清器股份有限公司 | Modified volcanic-rock acid-resistant adsorbent |
| CN104888712A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Recyclable adsorbent with good separation effect |
| CN104888731A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Composite adsorbent with good adsorption performance |
| CN104907039A (en) * | 2015-05-21 | 2015-09-16 | 安徽凤凰滤清器股份有限公司 | Composite volcanic rock absorbent |
| CN104888734A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Green environmentally-friendly modified volcanic rock adsorbent |
| CN104907043A (en) * | 2015-05-21 | 2015-09-16 | 安徽凤凰滤清器股份有限公司 | Modified volcanic rock adsorbent capable of recovering carbon monoxide |
| CN104888701A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Adsorbent capable of purifying air |
| CN104888687A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Volcanic rock composite adsorbent with good bactericidal activity and stability |
| CN104923155A (en) * | 2015-05-21 | 2015-09-23 | 安徽凤凰滤清器股份有限公司 | Desulfurizer adsorbent and preparation method thereof |
| CN104907040A (en) * | 2015-05-21 | 2015-09-16 | 安徽凤凰滤清器股份有限公司 | Rare-earth element added volcanic rock adsorbent |
| CN104888732A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Flavor-cleaning deodorizing adsorbent and preparation method thereof |
| CN104888733A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Adsorbent able to purify water |
| CN104888700A (en) * | 2015-05-21 | 2015-09-09 | 安徽凤凰滤清器股份有限公司 | Formaldehyde adsorbent and preparation method thereof |
| CN110713216A (en) * | 2019-10-24 | 2020-01-21 | 北京石油化工学院 | A multi-stage filtration system for high concentration oily sewage treatment |
-
1997
- 1997-07-15 CN CN 97112251 patent/CN1109654C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1171370A (en) | 1998-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1109654C (en) | Process for using petro-chemical mud to prepare adsorbent used to recover oil on water surface | |
| CN110240386B (en) | Straw and sludge cooperative treatment device and method | |
| CN110918061B (en) | Biomass waste activated carbon, preparation method thereof and application of biomass waste activated carbon in treatment of nitrophenol compounds in wastewater | |
| CN102276237B (en) | Attapulgite-based carbon composite ceramic particles and preparation method and use thereof | |
| Wang et al. | Effects of pyrolysis temperature and holding time on physicochemical properties of swine-manure-derived biochar | |
| CN110227534A (en) | A kind of magnetic N doping biology Pd/carbon catalyst and preparation method thereof based on sludge | |
| CN111453727B (en) | Preparation method of sludge-straw composite biomass activated carbon | |
| CN108927109B (en) | Method for modifying biochar by using phosphogypsum and application of biochar | |
| CN1306010C (en) | Process for producing gasoline, diesel oil and active carbon by using waste rubbers | |
| CN102765866A (en) | Method for recycling urban sludge | |
| CN108059160A (en) | A kind of carbonizing apparatus used in the production method and this method of bamboo charcoal | |
| CN113120898A (en) | Nitrogen-doped formed biochar and preparation method and application thereof | |
| CN107555414B (en) | Garden waste biomass charcoal and preparation method and application thereof | |
| Saleh et al. | Mg-modified sugarcane bagasse biochar for dual removal of ammonium and phosphate ions from aqueous solutions | |
| CN109942163B (en) | Method and system for preparing carbon by biological modification of sludge | |
| CN110835172A (en) | Method for preparing eutrophic water body remediation material by using decolored waste soil | |
| CN115010524A (en) | Modified biochar for reducing greenhouse gas emission in sludge composting process and preparation method and application method thereof | |
| CN100551520C (en) | Tar absorption dehydration purifier | |
| Mehrabinia et al. | Examining nitrate surface absorption method from polluted water using activated carbon of agricultural wastes | |
| CN113522240A (en) | Method for preparing desulfurization activated carbon by solid-phase hydrothermal modified biochar | |
| CN210367387U (en) | System for biological modification preparation charcoal of mud | |
| CN110295077A (en) | A kind of regenerated clean fuel and its manufacturing method with oily sludge production | |
| CN201625658U (en) | Organic waste cracking and carbonizing system with novel tail gas treating device | |
| CN115920840A (en) | Sludge-based activated carbon adsorbent and preparation method and application thereof | |
| CN109382073B (en) | Preparation method and application of alkali fusion fly ash modified pig manure biochar |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |