CN103979768A - Method for tempering oily sludge blended with coal water slurry - Google Patents
Method for tempering oily sludge blended with coal water slurry Download PDFInfo
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Abstract
The invention discloses a method for tempering oily sludge blended with coal water slurry. A fluorine-containing water-soluble macromolecule copolymer and a surfactant are dorpwise added for tempering treatment in the oily sludge centrifugal reduction treatment process; polyol ester lubricating oil, a polysulfide lubricating oil and a polyolefin drag reducing agent are added into the oily sludge subjected to the reduction treatment; and ultrasonically intensified mass transfer dispersion is carried to finally obtain the tempered oily sludge. The oily sludge tempering equipment needed in the method is simple, the treatment efficiency is high, the tempered oily sludge can be directly added into a conventional coal water slurry preparation system for preparing coal water slurry which has relatively high slurry concentration, good flowability and relatively good slurry preparation stability; therefore, relatively high industrial application values are achieved, meanwhile a guarantee is provided for harmless treatment and resource utilization of the oily sludge, and remarkable comprehensive economic and environmental-friendly benefits are achieved.
Description
Technical field
The invention belongs to contained Mud Treatment Technology field, be specifically related to a kind of oily sludge hardening and tempering method that can be used for mixing water distribution coal slurry.
Background technology
Coal water slurry is by a certain percentage through mixed a kind of novel, efficient, the clean coal derived fuel of physical grinding by coal, water and additive, coal water slurry has the features such as efficiency of combustion is high, pollutant emission is low, can be used for station boiler, Industrial Boiler and Industrial Stoves for oil, for gas, for coal combustion, is the important component part of current clean coal technology.Being mainly used in pressing gas in China's coal water slurry and preparing synthetic gas and then carry out synthetic ammonia and methanol industry, is the tap of Chemical Industry.Coal water slurry requires good pulping process, and the coal water slurry that need to make has higher coal-water fluid concentration, certain viscosity keeps good characteristic to ensure good mobility, preferably stability and suitable size distribution to ensure coal water slurry in the time gasifying, burn.Therefore suitable coal, additive and technique with slurry just seem very important for the slurrying of coal water slurry.
The main component of greasy filth is oil, water and mud, it has good calorific value and gas making performance, if greasy filth is mixed and is joined with coal, additive and water by a certain percentage, be mixed with the laggard promoting the circulation of qi of coal water slurry of sludge containing, the petroleum resources that are difficult in conventional greasy filth treatment process utilize can be converted into synthetic gas, and under 1300 DEG C of pyroprocessing, greasy filth thoroughly being carried out to harmless treatment, remaining silt is converted into ash content can cement processed.Therefore, to mix that the gas making of water distribution coal slurry compares with current various greasy filth processing be the technological method that a kind of feasible process, economical, industrial prospect are good and can carry out to greasy filth recycling and harmless treatment to greasy filth.But greasy filth due to wide material sources, complicated component, system homogeneity is poor, dispersive ability is bad and contain the component such as a large amount of colloids and macromole organic matter, join as directly greasy filth and coal, water and additive mixed to carry out water-coal-slurry slurring and will affect greatly sludge forming performance and the stability of slurrying.Therefore, how greasy filth to be mixed to join under the condition that does not change existing water-coal-slurry slurring technique and enter CWS system and just become and can use Coal Gasification Technology to process the key of greasy filth.
US Patent No. 4642715 is developed the oil soil treatment technique of solvent extraction-oxide treatment combination, and after processing, residue can meet landfill environmental requirement, but exist, solvent usage quantity is large, cost is high, solvent recuperation easily causes the shortcomings such as secondary pollution.Chinese patent CN102351389, using greasy filth as coking raw material processing, although can make full use of greasy filth Crude Oil resource, impacts greatly coker, and the waste that petroleum resources coking valuable in greasy filth is also caused.Chinese patent CN201010183569.8 by greasy filth directly and coal, water and additive mix to join and enter coal pulverizer, although can carry out slurrying but the requirement of greasy filth composition is high, bad adaptability to greasy filth to greasy filth, cannot meet the water-coal-slurry slurring stability and the sludge forming performance requirement that cause greatly due to greasy filth component fluctuation in production reality.
Summary of the invention
Technical problem to be solved by this invention be to overcome greasy filth due to its wide material sources, complicated component, system homogeneity is poor, dispersive ability is bad and contain a large amount of colloids and macromole organic matter fraction, directly make an addition in existing water-coal-slurry slurring system, can cause mix join that the coal water slurry slurryability of greasy filth is bad, viscosity is high, to gasification burner tip serious wear, less stable, pulping system technology stability is impacted to the shortcomings such as larger, provide a kind of and greasy filth directly can be made an addition to the greasy filth pre-treatment hardening and tempering method in existing water-coal-slurry slurring system.
Solving the problems of the technologies described above adopted technical scheme is made up of following step:
1, minimizing separating treatment oily sludge
Greasy filth is injected to greasy filth concentration tank and carry out flocculating settling separation, after greasy filth concentration tank top water separates, re-injection to sewage work processes, bottom water contained oil sludge enters horizontal spiral centrifuge after mixing with adjusting material and separates, the add-on of adjusting material is 0.1%～5.0% of water contained oil sludge quality, parting liquid enters vacuum drum pressure filter and carries out press filtration, after the greasy filth cake that filter cake obtains with centrifugation mixes as pending greasy filth.
2, ultrasonic auxiliary modified
Pending greasy filth is sent in the modified tank of greasy filth with mechanical stirring and intensified by ultrasonic wave device, added the viscosity decreasing milling aid of pending greasy filth quality 0.5%～3.0%, under ul-trasonic irradiation, mechanical stirring to fully mixing, obtains the greasy filth after modified.
Above-mentioned adjusting material is the multipolymer of acrylamide and fluorinated acrylate or fluorine-containing methacrylate, polyoxyethylene ether or polyether glycol, weight-average molecular weight is 10000～200000 daltonian cationic polyacrylamides mixtures of 10:1～5:2 in mass ratio, described multipolymer weight-average molecular weight is 1000～200000 dalton, wherein contain molar fraction and be 95% acrylamide unit, described fluorinated acrylate can be specifically the misery ester of perfluoro propylene, perfluoro propylene acid butyl ester, perfluoro propylene acid pentyl ester, any one in perfluoro propylene heptyl heptylate, described fluorine-containing methacrylate can be specifically fluoro methacrylic heptyl heptylate, as dodecafluoroheptyl methacrylate, described polyoxyethylene ether can be specifically fatty alcohol-polyoxyethylene ether AEO-9 etc., polyether glycol can be specifically polyether glycol F-68, polyether glycol 330N, polyether glycol DL-400D, polyether glycol DL-1000D, polyether glycol MN-3050D etc.
Above-mentioned viscosity decreasing milling aid is polyol ester class lubricating oil and poly-alpha olefins, the two tertiary alkyl polysulfides mixture of 3:10:1～3 in mass ratio, described polyol ester class lubricating oil can be specifically PETO, tetramethylolmethane valerate, tetramethylolmethane octanoate, tricarboxymethyl propane oleate, TriMethylolPropane(TMP) valerate, any one in trimethylolpropane caprylate, poly-alpha olefins is provided by Daqing petrochemical company limited of CNPC, two described tertiary alkyl polysulfides can be specifically commercial TPS20, TPS40 or TPS60 (being provided by company of Total France).
Beneficial effect of the present invention is as follows:
1, the present invention adds the fluorinated water soluble macromolecular multipolymer and the tensio-active agent that contain certain hydrophobic property in the centrifugal minimizing treating processes of greasy filth, make oil in greasy filth system, colloid, wax, bituminous matter and the composition of the sediment high dispersing, and form oil, water, mud three-phase stable homogeneous system, greatly reduce the generation being separated.
2, the present invention adds polyol ester class lubricating oil, polysulfide lubricant and polyolefins flow improver in minimizing greasy filth after treatment, make the viscosity of greasy filth greatly reduce and improve mobility, ensured that greasy filth is mixing slurry performance and the flowing property in preparation coal water slurry process with coal.And owing to having added lubricant composition that the component such as the grains of sand, metallic particles in greasy filth is reduced the wearing and tearing of burner in follow-up vapourizing furnace, effectively protect burner, improved the operation stability of mixing the coal water slurry gasifying device of joining greasy filth.
3, greasy filth quenching and tempering device required for the present invention is simple, processing efficiency is high, greasy filth after modified and coal, water and additive enter Mill Systems and can be separated into rapidly small profit mud particulate and fully mix with coal after mixing and joining, do not change existing pulping process, can make there is higher coal-water fluid concentration, good mobility and the better coal water slurry of pulping stability, there is higher industrial application value.And the greasy filth that does not carry out modifier treatment, as directly mixed water distribution coal slurry, in pulping process and the immovable situation of equipment, due to the impacts such as greasy filth viscosity, stability make to mix join the coal water slurry of greasy filth almost can not pulping.
4, the present invention carries out harmless treatment and recycling provides guarantee, economy and Environmental-protection comprehensive remarkable benefit for oily sludge.
Brief description of the drawings
Fig. 1 is process flow diagram of the present invention.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in more detail, but protection scope of the present invention is not limited only to these embodiment.
Embodiment 1
At the bottom of " three mud " being produced taking North Shaanxi sewage from oil refinery workshop and North Shaanxi oil recovery factory joint station crude settling tank greasy filth in mass ratio the mixed greasy filth of 1:6 as example, its initial water content is 60%, containing oily substance 30%, silt content is 10%, and concrete hardening and tempering method is as follows:
1, minimizing separating treatment oily sludge
As shown in Figure 1, greasy filth is injected to greasy filth concentration tank 2 with slush pump 1, and the weight-average molecular weight that adds oily sludge quality 0.3% is that 10000 daltonian zwitter-ion polyacrylamides carry out settlement separate, leave standstill after 6 hours, after greasy filth concentration tank 2 top water are separated, re-injection to sewage work processes, bottom water contained oil sludge enters horizontal spiral centrifuge 3 and carries out solid-liquid separation after mixing with adjusting material, described adjusting material is that weight-average molecular weight is the misery ester copolymer of 4000 daltonian acrylamide-perfluoro propylene (wherein contains molar fraction be 95% acrylamide unit), fatty alcohol-polyoxyethylene ether AEO-9, weight-average molecular weight is the 200000 daltonian cationic polyacrylamides mixtures of 10:3:2 in mass ratio, its add-on is 0.5% of water contained oil sludge quality, obtain greasy filth cake and parting liquid, gained greasy filth cake water content is 40%, oleaginousness is 40%, silt content is 20%, gained parting liquid carries out press filtration with vacuum drum pressure filter 4, filtrate is returned to sewage work and is processed, after filter cake mixes with greasy filth cake as pending greasy filth.
2, ultrasonic auxiliary modified
Pending greasy filth is sent in the modified tank 6 of greasy filth with mechanical stirring and intensified by ultrasonic wave device with worm conveyor 5, add the viscosity decreasing milling aid of pending greasy filth quality 1.2%, described viscosity decreasing milling aid is that trimethylolpropane caprylate, poly-alpha olefins, two tertiary alkyl polysulfide TPS40 are the mixture of 3:10:3 in mass ratio, be mechanical stirring 30 minutes under the intensified by ultrasonic wave effect that is 100MHz of 10kW, frequency at power, fully mix, obtain the greasy filth after modified.
The present embodiment weight-average molecular weight is that the misery ester copolymer of 4000 daltonian acrylamide-perfluoro propylene can be also that 1000 daltonian acrylamide-perfluoro propylene butyl acrylate copolymer are replaced by weight-average molecular weight, and also available weight-average molecular weight is that 10000 daltonian acrylamides-perfluoro propylene acid pentyl ester multipolymer or weight-average molecular weight are that 15000 daltonian acrylamide-perfluoro propylene heptyl heptylate multipolymers or weight-average molecular weight are that 20000 daltonian acrylamide-dodecafluoroheptyl methacrylate multipolymers are replaced.
Embodiment 2
Taking greasy filth at the bottom of North Shaanxi oil recovery factory joint station crude settling tank as example, its initial water content is 35%, and containing oily substance 40%, silt content is 25%, and concrete hardening and tempering method is as follows:
1, minimizing separating treatment oily sludge
As shown in Figure 1, greasy filth is injected to greasy filth concentration tank 2 with slush pump 1, and the weight-average molecular weight that adds oily sludge quality 0.3% is that 1400 daltonian zwitter-ion polyacrylamides carry out settlement separate, leave standstill after 10 hours, after greasy filth concentration tank 2 top water are separated, re-injection to sewage work processes, bottom water contained oil sludge enters horizontal spiral centrifuge 3 and carries out solid-liquid separation after mixing with adjusting material, described adjusting material is that weight-average molecular weight is 18000 daltonian acrylamide-dodecafluoroheptyl methacrylate multipolymers (wherein contain molar fraction be 95% acrylamide unit), polyether glycol F-68, weight-average molecular weight is the 10000 daltonian cationic polyacrylamides mixtures of 10:1:2 in mass ratio, its add-on is 1.0% of water contained oil sludge quality, obtain greasy filth cake and parting liquid, gained greasy filth cake water content is 35%, oleaginousness is 40%, silt content is 25%, gained parting liquid carries out press filtration with vacuum drum pressure filter 4, filtrate is returned to sewage work and is processed, after filter cake mixes with greasy filth cake as pending greasy filth.
2, ultrasonic auxiliary modified
Pending greasy filth is sent in the modified tank 6 of greasy filth with mechanical stirring and intensified by ultrasonic wave device with worm conveyor 5, add the viscosity decreasing milling aid of pending greasy filth quality 1.0%, described viscosity decreasing milling aid is that PETO, poly-alpha olefins, two tertiary alkyl polysulfide TPS20 are the mixture of 3:10:1 in mass ratio, be mechanical stirring 45 minutes under the intensified by ultrasonic wave effect that is 1.5MHz of 12kW, frequency at power, fully mix, obtain the greasy filth after modified.
The PETO of the present embodiment can be replaced with tetramethylolmethane valerate, and also available tetramethylolmethane octanoate or tricarboxymethyl propane oleate or TriMethylolPropane(TMP) valerate or trimethylolpropane caprylate are replaced.
Embodiment 3
In the minimizing separating treatment oily sludge step 1 of embodiment 1, adjusting material used with weight-average molecular weight be 6000 daltonian acrylamide-perfluoro propylene butyl acrylate copolymer, polyether glycol DL-400D, weight-average molecular weight be 10000 daltonian cationic polyacrylamides in mass ratio the mixture of 10:5:2 replace, its add-on is 5.0% of water contained oil sludge quality, other steps of this step are identical with embodiment 1, obtain pending greasy filth.In ultrasonic auxiliary modified step 2, for viscosity decreasing milling aid used, tetramethylolmethane octanoate, poly-alpha olefins, two tertiary alkyl polysulfide TPS60 are the mixture replacement of 3:10:2 in mass ratio, its add-on is pending greasy filth quality 0.5%, other steps of this step are identical with embodiment 1, obtain the greasy filth after modified.
Embodiment 4
In the minimizing separating treatment oily sludge step 1 of embodiment 1, adjusting material used with weight-average molecular weight be 15000 daltonian acrylamide-perfluoro propylene heptyl heptylate multipolymers, polyether glycol MN-3050D, weight-average molecular weight be 100000 daltonian cationic polyacrylamides in mass ratio the mixture of 10:3:2 replace, its add-on is 0.1% of water contained oil sludge quality, other steps of this step are identical with embodiment 1, obtain pending greasy filth.In ultrasonic auxiliary modified step 2, viscosity decreasing used for milling aid trimethylolpropane caprylate, poly-alpha olefins, two tertiary alkyl polysulfide TPS60 be in mass ratio 3:10:2 mixture replace, its add-on is pending greasy filth quality 3.0%, other steps of this step are identical with embodiment 1, obtain the greasy filth after modified.
What more than enumerate is only specific embodiments of the invention, those skilled in the art on the basis of the disclosure of invention institute thinkable random variation all in protection scope of the present invention.
In order to prove beneficial effect of the present invention, contriver by embodiment 1 and embodiment 2 greasy filth after modified and coal, water and additive send into coal pulverizer and carry out water-coal-slurry slurring, and taking oily sludge not modified in embodiment 1 and embodiment 2 as contrast, wherein greasy filth addition is 5% of total coal water slurry quality, additive addition is 0.3% of total coal water slurry quality, additive is poly-α-naphthalenesulfonicacid, and the coal water slurry test result making is in table 1.
Table 1 greasy filth is mixed water distribution coal slurry test result
From table 1, greasy filth after the inventive method modifier treatment directly and coal mix prepare coal water slurry functional, can be used for next step gasification, and combustion.
Claims (3)
1. for mixing a greasy filth hardening and tempering method for water distribution coal slurry, it is characterized in that it is made up of following step:
(1) minimizing separating treatment oily sludge
Greasy filth is injected to greasy filth concentration tank (2) and carry out flocculating settling separation, after greasy filth concentration tank (2) top water separates, re-injection to sewage work processes, bottom water contained oil sludge enters horizontal spiral centrifuge (3) after mixing with adjusting material and separates, the add-on of adjusting material is 0.1%～5.0% of water contained oil sludge quality, parting liquid enters vacuum drum pressure filter (4) and carries out press filtration, after the greasy filth cake that filter cake obtains with centrifugation mixes as pending greasy filth;
Above-mentioned adjusting material is that multipolymer, polyoxyethylene ether or polyether glycol, the weight-average molecular weight of acrylamide and fluorinated acrylate or fluorine-containing methacrylate is 10000～200000 daltonian cationic polyacrylamides mixtures of 10:1～5:2 in mass ratio, described multipolymer weight-average molecular weight is 1000～20000, wherein contains molar fraction and be 95% acrylamide unit;
(2) ultrasonic auxiliary modified
Pending greasy filth is sent in the modified tank of greasy filth (6) with mechanical stirring and intensified by ultrasonic wave device, add the viscosity decreasing milling aid of pending greasy filth quality 0.5%～3.0%, under ul-trasonic irradiation, mechanical stirring is to fully mixing, and obtains the greasy filth after modified;
Above-mentioned viscosity decreasing milling aid is polyol ester class lubricating oil and poly-alpha olefins, the two tertiary alkyl polysulfides mixture of 3:10:1～3 in mass ratio.
2. according to claim 1 for mixing the greasy filth hardening and tempering method of water distribution coal slurry, it is characterized in that: described fluorinated acrylate is any one in the misery ester of perfluoro propylene, perfluoro propylene acid butyl ester, perfluoro propylene acid pentyl ester, perfluoro propylene heptyl heptylate, and described fluorine-containing methacrylate is fluoro methacrylic heptyl heptylate.
3. according to claim 1 for mixing the greasy filth hardening and tempering method of water distribution coal slurry, it is characterized in that: described polyol ester class lubricating oil is any one in PETO, tetramethylolmethane valerate, tetramethylolmethane octanoate, tricarboxymethyl propane oleate, TriMethylolPropane(TMP) valerate, trimethylolpropane caprylate.
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| CN105859067A (en) * | 2016-04-20 | 2016-08-17 | 陕西延长石油（集团）有限责任公司 | Oil sludge pour point depressant |
| CN107022387A (en) * | 2017-04-20 | 2017-08-08 | 福建清源科技有限公司 | A kind of sludge water-coal-slurry of sludge height incorporation and preparation method thereof |
| CN107164003A (en) * | 2017-04-21 | 2017-09-15 | 华北电力大学（保定） | Improve the method for sludge water-coal-slurry paste-forming properties using ultrasonic wave breaking sludge floc sedimentation |
| CN111841408A (en) * | 2020-07-20 | 2020-10-30 | 中国海洋石油集团有限公司 | Pulping method containing polymer-containing oil sludge |
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| CN113667520A (en) * | 2021-07-13 | 2021-11-19 | 浙江大学 | Hydrophilic solid waste treatment and resource utilization method |
| CN114573213A (en) * | 2022-05-07 | 2022-06-03 | 北京中科环通工程科技有限公司 | Treating agent and treating method for treating oily sludge |
| CN115259592A (en) * | 2022-08-03 | 2022-11-01 | 西北化工研究院有限公司 | Method for cooperatively treating tank bottom slag oil sludge and chemical sludge filter cake |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111841408A (en) * | 2020-07-20 | 2020-10-30 | 中国海洋石油集团有限公司 | Pulping method containing polymer-containing oil sludge |
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| CN112143535B (en) * | 2020-09-25 | 2022-11-01 | 江苏天脉化工有限公司 | Coal water slurry additive and preparation method thereof |
| CN113667520A (en) * | 2021-07-13 | 2021-11-19 | 浙江大学 | Hydrophilic solid waste treatment and resource utilization method |
| CN114573213A (en) * | 2022-05-07 | 2022-06-03 | 北京中科环通工程科技有限公司 | Treating agent and treating method for treating oily sludge |
| CN115259592A (en) * | 2022-08-03 | 2022-11-01 | 西北化工研究院有限公司 | Method for cooperatively treating tank bottom slag oil sludge and chemical sludge filter cake |
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