CN103979768B - Method for tempering oily sludge blended with coal water slurry - Google Patents
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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 pressurized coal gasification in China's coal water slurry to prepare synthetic gas and then carry out synthetic ammonia and methanol industry, is the tap of Chemical Industry.Coal water slurry requires good pulping process, need obtained coal water slurry have higher coal-water fluid concentration, certain viscosity with ensure good mobility, preferably stability and suitable size distribution with ensures coal water slurry gasifying, burn time keep good characteristic.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 carried out mixing joining 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 being difficult in conventional oil-sludge treatment method utilize can be converted into synthetic gas, and under 1300 DEG C of pyroprocessing, thoroughly harmless treatment being carried out to greasy filth, remaining silt is converted into ash content can cement processed.Therefore, greasy filth is mixed that the gas making of water distribution coal slurry is a kind of feasible process compared with current various oil-sludge treatment, economical, industrial prospect are good and can be carried out the technological method of 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 containing components such as a large amount of colloids and macromole are organic, as direct greasy filth and coal, water and additive mixed to join and carries out water-coal-slurry slurring and will affect sludge forming performance and the stability of slurrying greatly.Therefore, how greasy filth to be mixed to join under the condition not changing existing water-coal-slurry slurring technique and enter CWS system and just become the key that can use Coal Gasification Technology process greasy filth.
US Patent No. 4642715 develops the oil soil treatment technique of solvent extraction-oxide treatment combination, and after process, residue can meet landfill environmental requirement, but has that solvent usage quantity is large, cost is high, solvent recuperation easily causes the shortcomings such as secondary pollution.Greasy filth as coking raw material process, although can make full use of greasy filth Crude Oil resource, impacts large to coker by Chinese patent CN102351389, and by waste that petroleum resources coking valuable in greasy filth also causes.Chinese patent CN201010183569.8 by greasy filth directly and coal, water and additive mix to join and enter coal pulverizer, although slurrying can be carried out to greasy filth but greasy filth component requirements is high, bad adaptability to greasy filth, the water-coal-slurry slurring stability and sludge forming performance requirement that cause because greasy filth component fluctuation is large in production reality cannot be met.
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 containing a large amount of colloids and macromole organic matter fraction, directly make an addition in existing water-coal-slurry slurring system to cause and mix that the coal water slurry slurryability of joining greasy filth is bad, viscosity is high, to gasification burner tip serious wear, less stable, the shortcomings such as larger are impacted to pulping system technology stability, a kind of greasy filth pre-treatment hardening and tempering method that greasy filth directly can be made an addition in existing water-coal-slurry slurring system is provided.
Solve the problems of the technologies described above adopted technical scheme to be made up of following step:
1, minimizing separating treatment oily sludge
Greasy filth is injected greasy filth concentration tank and carry out flocculation deposition seperation, after greasy filth concentration tank top water is separated, re-injection processes to sewage work, bottom water contained oil sludge enters horizontal spiral centrifuge after mixing with adjusting material and is separated, 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, as pending greasy filth after the greasy filth cake that filter cake and centrifugation obtain mixes.
2, ultrasonic wave added is modified
Pending greasy filth sent in the modified tank of greasy filth of band 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, obtain modified after greasy filth.
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 the mixture of 10000 ~ 200000 daltonian cationic polyacrylamides 10:1 ~ 5:2 in mass ratio, described multipolymer weight-average molecular weight is 1000 ~ 200000 dalton, wherein containing molar fraction is the acrylamide unit of 95%, described fluorinated acrylate can be specifically perfluoro octyl ester, perfluoro propylene acid butyl ester, perfluoro propylene acid pentyl ester, any one in perfluoro propylene heptyl heptylate, described fluorine-containing methacrylate can be specifically fluoromethyl heptylacrylate, 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 mixture of two tertiary alkyl polysulfides 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 tensio-active agent that contain certain hydrophobic property in greasy filth centrifugal minimizing treating processes, 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 be separated.
2, the present invention adds polyol ester class lubricating oil, polysulfide lubricant and polyolefins flow improver in the greasy filth after minimizing process, make the viscosity of greasy filth greatly reduce and improve mobility, ensure that greasy filth prepares slurry performance in coal water slurry process and flowing property mixing with coal.And owing to adding lubricant composition, 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, improve the operation stability 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 oily cement grains and fully mix with coal after mixing and joining, do not change existing pulping process, the coal water slurry with higher coal-water fluid concentration, good mobility and better pulping stability can be obtained, there is higher industrial application value.And do not carry out the greasy filth of modifier treatment, as directly mixed water distribution coal slurry, under pulping process and the immovable situation of equipment, due to the impact such as greasy filth viscosity, stability makes to mix the coal water slurry of joining greasy filth almost can not pulping.
4, the present invention is that oily sludge carries out harmless treatment and recycling provides guarantee, economy and Environmental-protection comprehensive remarkable benefit.
Accompanying drawing explanation
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 embodiments.
Embodiment 1
The greasy filth mixed greasy filth of 1:6 in mass ratio at the bottom of " three mud " that produces for North Shaanxi sewage from oil refinery workshop and North Shaanxi oil recovery factory joint station crude settling tank, 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 slush pump 1 is injected greasy filth concentration tank 2, and the weight-average molecular weight adding oily sludge quality 0.3% is 10000 daltonian zwitter-ion polyacrylamides carries out settlement separate, leave standstill after 6 hours, after greasy filth concentration tank 2 top water being separated, re-injection processes to sewage work, enter horizontal spiral centrifuge 3 after bottom water contained oil sludge mixes with adjusting material and carry out solid-liquid separation, described adjusting material is weight-average molecular weight is 4000 daltonian acrylamide-perfluoro octyl ester copolymers (wherein containing molar fraction is the acrylamide unit of 95%), fatty alcohol-polyoxyethylene ether AEO-9, weight-average molecular weight is the mixture of 200000 daltonian cationic polyacrylamides 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 vacuum drum pressure filter 4 carries out press filtration, filtrate returns sewage work's process, as pending greasy filth after filter cake mixes with greasy filth cake.
2, ultrasonic wave added is modified
Pending greasy filth worm conveyor 5 is sent in the modified tank 6 of greasy filth of band mechanical stirring and intensified by ultrasonic wave device, add the viscosity decreasing milling aid of pending greasy filth quality 1.2%, described viscosity decreasing milling aid is trimethylolpropane caprylate, poly-alpha olefins, two tertiary alkyl polysulfide TPS40 is the mixture of 3:10:3 in mass ratio, power be 10kW, frequency be 100MHz intensified by ultrasonic wave effect under mechanical stirring 30 minutes, fully mix, obtain modified after greasy filth.
The present embodiment weight-average molecular weight is 4000 daltonian acrylamide-perfluoro octyl ester copolymers can be also that 1000 daltonian acrylamides-perfluoro propylene butyl acrylate copolymer are replaced by weight-average molecular weight, and also available weight-average molecular weight is 10000 daltonian acrylamides-perfluoro propylene acid pentyl ester multipolymer or weight-average molecular weight be 15000 daltonian acrylamide-perfluoro propylene heptyl heptylate multipolymers or weight-average molecular weight is 20000 daltonian acrylamides-dodecafluoroheptyl methacrylate multipolymer replacement.
Embodiment 2
For greasy filth at the bottom of North Shaanxi oil recovery factory joint station crude settling tank, 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 slush pump 1 is injected greasy filth concentration tank 2, and the weight-average molecular weight adding oily sludge quality 0.3% is 1400 daltonian zwitter-ion polyacrylamides carries out settlement separate, leave standstill after 10 hours, after greasy filth concentration tank 2 top water being separated, re-injection processes to sewage work, enter horizontal spiral centrifuge 3 after bottom water contained oil sludge mixes with adjusting material and carry out solid-liquid separation, described adjusting material is weight-average molecular weight is 18000 daltonian acrylamide-dodecafluoroheptyl methacrylate multipolymers (wherein containing molar fraction is the acrylamide unit of 95%), polyether glycol F-68, weight-average molecular weight is the mixture of 10000 daltonian cationic polyacrylamides 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 vacuum drum pressure filter 4 carries out press filtration, filtrate returns sewage work's process, as pending greasy filth after filter cake mixes with greasy filth cake.
2, ultrasonic wave added is modified
Pending greasy filth worm conveyor 5 is sent in the modified tank 6 of greasy filth of band mechanical stirring and intensified by ultrasonic wave device, add the viscosity decreasing milling aid of pending greasy filth quality 1.0%, described viscosity decreasing milling aid is PETO, poly-alpha olefins, two tertiary alkyl polysulfide TPS20 is the mixture of 3:10:1 in mass ratio, power be 12kW, frequency be 1.5MHz intensified by ultrasonic wave effect under mechanical stirring 45 minutes, fully mix, obtain modified after greasy filth.
The PETO of the present embodiment can be replaced with tetramethylolmethane valerate, also available tetramethylolmethane octanoate or tricarboxymethyl propane oleate or TriMethylolPropane(TMP) valerate or trimethylolpropane caprylate replacement.
Embodiment 3
In the minimizing separating treatment oily sludge step 1 of embodiment 1, adjusting material weight-average molecular weight used is 6000 daltonian acrylamide-perfluoro propylene butyl acrylate copolymer, polyether glycol DL-400D, weight-average molecular weight be 10000 daltonian cationic polyacrylamides in mass ratio 10:5:2 mixture 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 the modified step 2 of ultrasonic wave added, viscosity decreasing milling aid tetramethylolmethane octanoate used, poly-alpha olefins, two tertiary alkyl polysulfide TPS60 are that the mixture of 3:10:2 is replaced in mass ratio, its add-on is pending greasy filth quality 0.5%, other steps of this step are identical with embodiment 1, obtain modified after greasy filth.
Embodiment 4
In the minimizing separating treatment oily sludge step 1 of embodiment 1, adjusting material weight-average molecular weight used is 15000 daltonian acrylamides-perfluoro propylene heptyl heptylate multipolymer, polyether glycol MN-3050D, weight-average molecular weight be 100000 daltonian cationic polyacrylamides in mass ratio 10:3:2 mixture 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 the modified step 2 of ultrasonic wave added, viscosity decreasing milling aid trimethylolpropane caprylate used, poly-alpha olefins, two tertiary alkyl polysulfide TPS60 are that the mixture of 3:10:2 is replaced in mass ratio, its add-on is pending greasy filth quality 3.0%, other steps of this step are identical with embodiment 1, obtain modified after greasy filth.
More than enumerate be only specific embodiments of the invention son, 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 modified after greasy filth and coal, water and additive send into coal pulverizer and carry out water-coal-slurry slurring, and with oily sludge not modified in embodiment 1 and embodiment 2 for 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 obtained coal water slurry test result is in table 1.
Water distribution coal slurry test result mixed by table 1 greasy filth
From table 1, the greasy filth after the inventive method modifier treatment directly and coal to mix the coal water slurry prepared 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 greasy filth concentration tank (2) and carry out flocculation deposition seperation, after greasy filth concentration tank (2) top water is separated, re-injection processes to sewage work, bottom water contained oil sludge enters horizontal spiral centrifuge (3) and is separated after mixing with adjusting material, 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, as pending greasy filth after the greasy filth cake that filter cake and centrifugation obtain mixes;
Above-mentioned adjusting material is the multipolymer of acrylamide and fluorinated acrylate or fluorine-containing methacrylate, one of polyoxyethylene ether or polyether glycol and weight-average molecular weight be 10000 ~ 200000 daltonian cationic polyacrylamide 10:(1 ~ 5 in mass ratio): 2 mixtures formed, described multipolymer weight-average molecular weight is 1000 ~ 20000, and wherein containing molar fraction is the acrylamide unit of 95%;
(2) ultrasonic wave added is modified
Pending greasy filth is sent in the modified tank of greasy filth (6) of band 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, obtain modified after greasy filth;
Above-mentioned viscosity decreasing milling aid is the mixture of polyol ester class lubricating oil and poly-alpha olefins, two tertiary alkyl polysulfides 3:10:1 ~ 3 in mass ratio.
2. the greasy filth hardening and tempering method for mixing water distribution coal slurry according to claim 1, it is characterized in that: described fluorinated acrylate is perfluoro octyl ester, perfluoro propylene acid butyl ester, perfluoro propylene acid pentyl ester, any one in perfluoro propylene heptyl heptylate, and described fluorine-containing methacrylate is fluoromethyl heptylacrylate.
3. the greasy filth hardening and tempering method for mixing water distribution coal slurry according to claim 1, 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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| CN104212502A (en) * | 2014-08-17 | 2014-12-17 | 青岛蓬勃石油技术服务有限公司 | Petroleum product composite additive and preparation method thereof |
| 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 |
| 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 |
| CN113667520B (en) * | 2021-07-13 | 2022-09-09 | 浙江大学 | Hydrophilic solid waste treatment and resource utilization method |
| CN114573213B (en) * | 2022-05-07 | 2022-07-22 | 北京中科环通工程科技有限公司 | Treating agent and treating method for oily sludge treatment |
| CN115259592B (en) * | 2022-08-03 | 2023-06-16 | 西北化工研究院有限公司 | Method for cooperatively disposing tank bottom slag oil sludge and chemical sludge filter cake |
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