CN108526192B - Method for treating oil-containing solid waste and additive used by same - Google Patents
Method for treating oil-containing solid waste and additive used by same Download PDFInfo
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- CN108526192B CN108526192B CN201810230037.1A CN201810230037A CN108526192B CN 108526192 B CN108526192 B CN 108526192B CN 201810230037 A CN201810230037 A CN 201810230037A CN 108526192 B CN108526192 B CN 108526192B
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- 239000000654 additive Substances 0.000 title claims abstract description 121
- 230000000996 additive effect Effects 0.000 title claims abstract description 114
- 239000002910 solid waste Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000010438 heat treatment Methods 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 17
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000003921 oil Substances 0.000 claims description 57
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 26
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 20
- 239000003822 epoxy resin Substances 0.000 claims description 19
- 229920000647 polyepoxide Polymers 0.000 claims description 19
- 229920000057 Mannan Polymers 0.000 claims description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000005011 phenolic resin Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229920002472 Starch Polymers 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- 239000008107 starch Substances 0.000 claims description 8
- 235000019698 starch Nutrition 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 229910052810 boron oxide Inorganic materials 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 7
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 7
- 150000004676 glycans Chemical class 0.000 claims description 7
- 229920001282 polysaccharide Polymers 0.000 claims description 7
- 239000005017 polysaccharide Substances 0.000 claims description 7
- 229920002307 Dextran Polymers 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims 1
- 238000011282 treatment Methods 0.000 abstract description 48
- 239000002699 waste material Substances 0.000 description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 32
- 239000010779 crude oil Substances 0.000 description 19
- 238000005553 drilling Methods 0.000 description 17
- 238000009826 distribution Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 11
- 229920001568 phenolic resin Polymers 0.000 description 11
- 239000000571 coke Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 229920001503 Glucan Polymers 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000001488 sodium phosphate Substances 0.000 description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 235000013361 beverage Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000013021 overheating Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000005672 electromagnetic field Effects 0.000 description 3
- 239000005007 epoxy-phenolic resin Substances 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 238000004017 vitrification Methods 0.000 description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- FYGDTMLNYKFZSV-URKRLVJHSA-N (2s,3r,4s,5s,6r)-2-[(2r,4r,5r,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5r,6s)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1[C@@H](CO)O[C@@H](OC2[C@H](O[C@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-URKRLVJHSA-N 0.000 description 1
- 229920000310 Alpha glucan Polymers 0.000 description 1
- 229920002498 Beta-glucan Polymers 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 235000020965 cold beverage Nutrition 0.000 description 1
- 235000021270 cold food Nutrition 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- -1 that is Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
Landscapes
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a method for treating oil-containing solid waste and an additive used by the method. Wherein, the additive comprises: 1 to 99 weight percent of high molecular polymer and 1 to 99 weight percent of solid inorganic matter; wherein the inorganic substance is one or more of inorganic salt and salified oxide. A method of treating oily solid waste, comprising: uniformly mixing the additive and the oily solid waste, wherein the weight of the additive is 1-35% of the weight of the mixture of the additive and the oily solid waste; and putting the mixed materials into a resonant cavity of microwave equipment, and heating by using microwaves. When the oily solid waste is treated, the additive is uniformly mixed with the oily solid waste and then subjected to microwave treatment, so that the microwave can be uniformly distributed under the condition of high deoiling rate, and the phenomenon of nonuniform heating is avoided.
Description
Technical Field
The invention relates to a method for treating oil-containing solid waste and an additive used by the method, belonging to the technical field of petrochemical industry.
Background
Oil extraction, oil refining and other petrochemical related fields generate a large amount of oil-containing solid waste. If the oily solid waste is directly discharged without being treated, on one hand, the environment is seriously influenced, and on the other hand, the resource waste is caused, so that the realization of the harmlessness and the resource utilization of the oily solid waste is the final aim of the current research.
At present, the treatment method of the oily solid waste mainly comprises the following steps: the processes of reinjection, solidification, mechanical separation, cleaning, biological, solvent extraction, and thermochemical treatment. The final purpose is to realize the reduction, harmlessness and reclamation of the oily waste. The treatment aspects all have certain defects, such as land occupation by a landfill method and a solidification method, potential environmental pollution hazards and resource waste. The treatment period of the biological method is long, and the content of residual oil is difficult to reach the standard. Extraction methods require large amounts of solvent. The traditional heat treatment method comprises an incineration method and a thermal desorption method, wherein waste gas and waste residue are discharged in the incineration method, and the common thermal desorption method can recover organic matters to realize resource utilization and harmlessness, but the traditional thermal desorption method has high energy consumption and long treatment time at present.
The prior art also mentions a method for treating oily solid waste by using microwave, and specifically, a method for heating oily waste to 200 to 900 ℃ by using microwave, thereby pyrolyzing the oily waste to generate oil gas for recycling. However, the treatment of the oily solid waste by this method requires at least 4 hours, and the deoiling rate of the oily solid waste is not yet 66%.
In order to increase the deoiling rate of the oily solid waste, some researches have attempted to add activated carbon to the oily solid waste, such as crude oil waste. However, although the deoiling rate can be increased by adding activated carbon to the crude oil-containing waste, the uniformity of microwave distribution cannot be improved, and a local overheating phenomenon often occurs during microwave heating.
Disclosure of Invention
The present invention provides a method for treating oil-containing solid waste and an additive used therein, so as to obtain high deoiling efficiency and reduce the occurrence of local overheating phenomenon.
According to some embodiments of the present invention, there is provided an additive for treating oily solid waste, the additive including, in weight percent: 1 to 99 percent of high molecular polymer and 1 to 99 percent of solid inorganic matter; wherein the inorganic substance is one or more of inorganic salt and salified oxide.
The additive as described above, wherein the high molecular polymer is one or more of polysaccharide high molecular polymer, epoxy resin and phenolic resin.
The additive as described above, wherein the polysaccharide high molecular polymer is one or more of dextran, mannan, starch and cellulose.
The additive as described above, wherein the salt-forming oxide is one or more of a basic oxide, an acidic oxide and an amphoteric oxide.
The additive as described above, wherein the basic oxide is one or more of iron oxide, calcium oxide and magnesium oxide.
The additive as described above, wherein the acidic oxide is one or more of silicon oxide and boron oxide.
The additive as described above, wherein the amphoteric oxide is one or more of alumina and titania.
The additive as described above, wherein the inorganic salt is a strong base weak acid salt. One or more of silicate and phosphate are preferable, but other strong and weak acid salts such as sodium carbonate, sodium bicarbonate, and sodium hypochlorite may be selected.
The additive may be a mixture of mannan and titanium oxide, for example, a mixture of 75 wt% mannan and 25 wt% titanium oxide, and the additive has simple components, and the mixture of mannan and titanium oxide can improve the uniformity of microwave distribution and the efficiency of converting microwave energy into heat energy, so as to reduce the occurrence of hot spots in the microwave heating process.
According to some embodiments of the present invention, there is provided a method of treating oil-containing solid waste, including:
uniformly mixing the additive and the oily solid waste, wherein the weight of the additive is 1-35% of the weight of the mixture of the additive and the oily solid waste;
and putting the mixed materials into a resonant cavity of microwave equipment, and heating by using microwaves.
The method as described above, wherein the weight of the additive is 5% to 30% of the weight of the mixture.
According to the technical scheme of the embodiment of the invention, the additive and the oily solid waste are uniformly mixed and then subjected to microwave treatment, so that the deoiling rate is high, the uniformity of microwave distribution can be improved, the mixture is uniformly heated, local hot spots are basically avoided, and the service life of microwave treatment equipment is prolonged.
Advantages of additional aspects of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
In the following, percentages are by weight unless otherwise specified.
The medium material can absorb microwave energy to different degrees, microwave heating is heating by utilizing the mutual coupling of the medium material and a microwave electromagnetic field, and has the characteristics of quick heating, high efficiency, uniform heating and the like, so the microwave heating is a very safe heating technology. For example, in daily life, a household microwave oven is generally used for heating cold food or beverages. The food or beverage is placed in a cavity of a microwave oven, after the microwave oven is started, microwaves emitted by a microwave source are fed into the cavity and are reflected for multiple times on the inner wall of the cavity, in the reflecting process, some microwaves penetrate through the food or beverage, high-frequency reciprocating motion of dipole molecules in the food or beverage is caused to generate friction, the temperature of the food or beverage is increased, and the heating mode can heat the inside and the outside of the food or beverage at the same time without any heat conduction.
Based on this, researchers hope to introduce the microwave heating mode into the field of petrochemical industry, especially into the treatment of oil-containing solid waste (such as crude oil waste, oil-containing drilling waste, and contaminated soil generated by the leakage of transportation or processing pipelines into soil) generated by oil extraction, refining and post-processing, so as to realize the rapid separation of oil in solid waste such as soil or sand grains, and the like, so as to reduce the pollution to the environment, and thus realize the green environmental protection of extraction, transportation and processing in the field of petrochemical industry.
However, the inventors have found, after intensive studies on the microwave treatment process disclosed in the prior art: because the composition of oil contained in different solid wastes is different, for example, oil-containing drilling wastes are generally single diesel oil, while the composition of crude oil wastes is more complex. Therefore, in order to separate more oil from the solid waste in order to obtain a higher oil removal rate when treating the solid waste, the oil-containing solid waste needs to reach a higher temperature in a short time in the microwave heating treatment, and the oil removal rate of directly microwave heating the oil-containing solid waste in the prior art is relatively low, for example, the oil removal rate of microwave heating treatment of crude oil waste is only 8.8%, and the oil removal rate of microwave heating treatment of oil-containing drilling waste is also only 65.60%. The inventors provided a method for increasing the deoiling rate by adding a certain amount of activated carbon to the crude oil waste in the previous application, however, the inventors found in the subsequent studies that the problem of uneven heating often occurs when the microwave heating treatment is performed after the activated carbon is added to the crude oil waste, resulting in the occurrence of the local overheating phenomenon (i.e., hot spots). The occurrence of the hot spots can cause the organic matters (mainly oil contained in solid waste) at the position to generate a pyrolysis reaction to generate coke, and the generated coke can further absorb microwaves to increase the temperature at the position, so that the heating uniformity is influenced, and a material vitrification phenomenon can be caused; and if the generated coke is deposited on the microwave equipment, hot spots can continuously appear at the deposition position in the subsequent microwave heating process, the heating uniformity in the subsequent treatment of the oily solid waste can be influenced, and even the whole microwave equipment can be damaged, so that the service life of the microwave equipment is obviously reduced. On the other hand, no matter crude oil waste or drilling waste, the microwave distribution at the material is not uniform due to the low dielectric constant of the material, and on the other hand, in order to improve the removal rate of oil products, the electric field intensity of the material is usually improved, and hot spots are inevitably formed under high electric field intensity.
In view of the above, the present invention provides an additive for adding to oily solid waste, the additive comprising 1-99% by weight of a high molecular polymer and 1-99% by weight of a solid inorganic substance, wherein the inorganic substance is one or more of an inorganic salt and a salt-forming oxide. In the treatment of the oily solid waste, the additive is uniformly mixed with the oily solid waste and then fed into a resonant cavity of a microwave heating device, wherein the resonant cavity can be a mono-mode resonant cavity or a multi-mode resonant cavity, for example, the multi-mode resonant cavity used in the following embodiments is a cuboid or cubic cavity, and the reactor used in the following embodiments is a cylindrical reactor, but those skilled in the art will understand that the following embodiments are also applicable to mono-mode resonant cavities and reactors of different shapes. Through uniformly mixing the additive into the oily solid waste, the microwave power density at the mixture is proposed to be higher than that of the oily solid waste without the additive, and experiments prove that the microwave power density can reach 10 at most9W/m3(tile/cubic meter), can also make the microwave distribution of mixture department even in addition to make the heating of this mixture even, avoided the emergence of local overheat phenomenon (also avoided the appearance of hot spot), avoided then among the microwave heating process because the hot spot appears and leads to the produced coke of organic matter pyrolysis, just also can not have the coke to adhere to on the inner wall of cylindrical reactor, and then avoided the coke to adhere to the harm of the lasting high temperature that appears to microwave heating equipment.
In the present invention, the high molecular polymer includes one or more of a polysaccharide high molecular polymer, an epoxy resin, and a phenol resin. In some alternative embodiments, the polysaccharide high molecular polymer may be one or more of dextran, mannan, starch and cellulose. Of course, any polymer with a suitable molecular weight can be selected in the present invention, such as alpha-glucan or beta-glucan with a molecular weight of 1000-10000, mannan with a molecular weight of 5000-10000, starch with a molecular weight of 10000-100000, cellulose with a molecular weight of 5000-100000, and phenolic resin with a molecular weight of 500-1000, which are available on the market. It should be noted that when the molecular weight of the selected high molecular polymer is larger, it is generally recommended to select a salt-forming oxide (such as calcium oxide) with larger polarity to match with the high molecular polymer, so as to be more beneficial to improve the capability of the material to absorb microwaves and convert the microwaves into heat energy, that is, to enable the additive to have higher microwave power density and more uniform microwave distribution after being mixed with the oily solid waste, so that the heating rate and the heating uniformity are better. When the additive contains an epoxy resin, an epoxy resin having an epoxy value of more than 0.25 may be selected, or a commercially available epoxy resin having an epoxy value of 0.25 to 0.45 may be selected. In some optional embodiments, an epoxy resin with a larger epoxy value may be selected, and when the epoxy resin with a larger epoxy value is selected, a material with a higher dielectric constant, such as titanium oxide, may be selected from the inorganic components to improve the microwave power density and the uniformity of microwave distribution at the position of the mixture after the additive is mixed with the oily solid waste, thereby improving the deoiling rate of the oily solid waste and avoiding the occurrence of uneven heating.
In the present invention, the inorganic salt may be a weak acid strong base salt such as sodium phosphate, potassium phosphate, sodium silicate, potassium silicate, sodium carbonate, sodium bicarbonate, sodium hypochlorite and the like. The salt-forming oxide may be one or more of an acidic oxide (e.g., silicon oxide and boron oxide), one or more of a basic oxide (e.g., iron oxide, magnesium oxide, and calcium oxide), one or more of an amphoteric oxide (e.g., aluminum oxide and titanium oxide), and, of course, a mixture of several of a basic oxide, an acidic oxide, and an amphoteric oxide. In some alternative embodiments, the components and weight ratio of the components of the additive can be properly matched so as to obtain a proper dielectric constant and dielectric loss of the additive, thereby improving the distribution uniformity of the microwave electromagnetic field and the heating efficiency of the microwave. For example, titanium oxide with a higher dielectric constant can be added to the additive to improve the microwave absorption ability of the additive, so that the mixture can have a more uniform microwave distribution after the additive is uniformly mixed with the oily solid waste, and the phenomenon of non-uniform heating can be avoided.
For example, the polymer in the additive of the present invention may be selected from one or more of polysaccharide polymer, epoxy resin and phenolic resin, and the inorganic substance may be selected from one or more of strong alkali weak acid salt, basic oxide, acidic oxide and amphoteric oxide. More specifically, the polymer in the additive of the present invention may be selected from one or more of dextran, mannan, starch, cellulose, epoxy resin and phenolic resin, and the inorganic substance may be selected from one or more of iron oxide, calcium oxide, magnesium oxide, silicon oxide, boron oxide, aluminum oxide, titanium oxide, sodium silicate and sodium phosphate. For example, in some alternative embodiments, the high molecular polymer may include epoxy resins, especially epoxy resins with high epoxy value, and aliphatic epoxy resins, that is, epoxy resins with carbon atoms at two ends of the epoxy group in the middle position are selected to increase the dielectric loss of the additive; the inorganic material may include titanium dioxide, which may provide better dielectric constant and dielectric loss by using epoxy resin and titanium dioxide, enhance the ability to absorb microwave energy and convert microwave energy into heat energy, and make the microwave distribution more uniform.
The power of the microwave in the present invention may be determined according to the implementation need and the application environment, and may be any value above 0.5kW, for example. Generally, 1kW, 3kW, 5kW or 15kW can be used for heating in the small-sized microwave heating, and 200kW or more can be used for heating when the treatment amount is large. The frequency of the microwave heating can be 300 MHz-300 GHz, but 915MHz and 2450MHz are generally adopted in the production process in order to avoid interference to satellite communication and radar, but it should be understood that other frequencies in 300 MHz-300 GHz can be adopted for microwave heating under the condition of adopting a certain shielding measure.
The invention adopts an ASTM D95 standard method to measure the water content of a sample, and particularly, the water content is measured by mixing and azeotroping about 20g of the sample with 100ml of toluene and then separating the water and the toluene. The sample oil content was determined using the methylene chloride extraction method described below.
In the invention, the method for calculating the deoiling rate v is as follows: before and after the reaction, the substances in the reactor of the resonant cavity are weighed, and the percentage content of the oil in the mixed materials and the remainder is analyzed by adopting a solvent extraction method.
V＝(a1/(100-s1-w1)-a2/(100-s1-w2))/a1/(100-s1-w1)
Wherein v is the oil removal rate (by weight), a1Is the mass percentage (dry basis) of oil in the mixed materials, a2Is the mass percent (dry basis) of oil in the remaining material after microwave heating, s1 is the percent of complexing agent added, w1 is the water content in the sample before microwave treatment, and w2 is the water content of the sample after microwave treatment.
Example 1
Several specific additives are provided below, but it should be understood by those skilled in the art that the present embodiment is not a specific limitation to the kind of the additive of the present invention, as long as 1 to 99 weight percent of the high molecular polymer and 1 to 99 weight percent of the inorganic salt, the salt-forming oxide or the combination of the inorganic salt and the salt-forming oxide are included, and the composition capable of satisfying the object of the present invention is within the protection scope of the present invention.
Additive a: 75% phenolic resin, 5% titanium oxide, 18% boron oxide and 2% alumina;
and (b) an additive: 75% of mannan, 25% of titanium oxide;
and (c) an additive: 25% cellulose, 75% sodium phosphate;
and (3) an additive d: 25% of phenolic resin, 25% of epoxy resin, 25% of starch and 25% of aluminum oxide;
and (e) an additive: 25% epoxy resin, 25% dextran, 20% silicon oxide, 10% iron oxide, 10% sodium phosphate, 10% sodium silicate.
And (3) an additive f: 1% dextran, 30% titanium oxide, 69% calcium oxide;
additive g: 75% of phenolic resin, 24% of glucan and 1% of silicon oxide;
and (4) an additive h: 50% of glucan, 30% of titanium oxide and 20% of magnesium oxide.
Specifically, the additives a to h can be prepared by directly stirring and mixing the components, and certainly, in industrial production or experiments, because the additives need to be uniformly mixed with the oily solid waste, the components can also be directly added into the oily solid waste and stirred to obtain a mixture of the additives and the oily solid waste. In addition, for the additive with a small amount of high molecular polymer, such as the additive f, the high molecular polymer can be soaked in other components after being dissolved by water, so that the purpose of uniformly dispersing the high molecular polymer in other components is achieved, then, moisture is removed in a drying or natural airing mode, and the like, and finally, all the components in the additive can be uniformly mixed, so that the absorption capacity of the mixture of the additive and the oily solid waste on microwaves is improved, and the microwaves are distributed more uniformly.
As can be seen from the following description of the embodiments, after the additive provided in this embodiment is added to the oily solid waste and uniformly mixed, the absorption capacity for microwaves can be improved and the microwave distribution is more uniform, so that the oily solid waste treated by microwaves can have a good deoiling rate and can be uniformly heated, no local hot spot occurs, and the microwave equipment can be prevented from being damaged.
Example 2
The method is characterized in that crude oil waste is taken as a treatment object, the oil content of the crude oil waste is 25.0%, the water content of the crude oil waste is 15.3%, microwave treatment is carried out in a cylindrical reactor of a single-mode resonant cavity, when microwaves with the power of 3KW and the frequency of 2450MHz are used for treating a sample for 50s, the deoiling rate of the sample is 8.8%.
When 5% by weight of activated carbon was added and mixed uniformly with the sample, the sample was treated with microwaves of the same power and frequency for 50 seconds, and the deoiling ratio of the sample was 89.9%.
When 5% by weight of additive b consisting of 75% mannan and 25% titanium oxide was added and mixed uniformly with the sample, the sample was treated with microwaves of the same power and frequency for 50s, and the deoiling ratio of the sample was 98.2%.
The weight of the mixture may be, for example, 100g, and the results are shown in Table 1 below:
table 1 results of treatment of example 2
As can be seen from the table above, the deoiling rate of the additive b is obviously higher than that of the activated carbon when the crude oil waste is treated by using microwaves with the power of 3KW and the frequency of 2450MHz for the same time.
In addition, the electromagnetic field distribution of the sample mixed with the activated carbon is not uniform in the microwave treatment process, so that hot spots exist in the sample, organic matters at the hot spots are further pyrolyzed, coke exists in a pyrolyzed product, and the coke is a good microwave absorbing substance and can further absorb microwavesAbsorb the microwave, make the temperature in hot spot department higher and higher, take place vitrification phenomenon at last, easily adhere to the inside of cylindrical reactor to be difficult to the clearance, along with the increase of number of times of use or live time, the reactor can receive serious destruction, leads to unable the use. But the sample mixed with the additive b can ensure that the microwave power density of the position of the sample is high (up to 10)8W/m3) And the microwave distribution is more uniform, thereby avoiding the local overheating phenomenon caused by nonuniform heating. Therefore, the sample mixed with the additive b is not substantially deposited on the inner surface of the cylindrical reactor after the microwave treatment, and thus the damage to the cylindrical reactor is reduced and the service life of the microwave treatment apparatus is increased.
Example 3
The method is characterized in that oil-containing drilling waste is taken as a treatment object, the oil content of the oil-containing drilling waste is 21.8%, the water content of the oil-containing drilling waste is 5.1%, microwave treatment is carried out in a cylindrical reactor of a multi-mode resonant cavity, when microwaves with the power of 5kW and the frequency of 2450MHz are used for treating a sample for 30s, the deoiling rate of the sample is 65.60%. It will be appreciated by those skilled in the art that the oil component in the oil-bearing drilling waste in this example is typically diesel, whereas the oil in the crude oil waste in example 2 is crude oil.
When 5% by weight of activated carbon was added and mixed uniformly with the sample, the sample was treated with microwaves of the same power and frequency for 30 seconds, and the deoiling ratio of the sample was 94.45%.
When 5% by weight of additive b consisting of 75% mannan and 25% titanium oxide was added and mixed uniformly with the sample, the sample was treated with microwaves of the same power and frequency for 30 seconds, and the deoiling ratio of the sample was 97.11%.
The weight of the mixture in this example may be, for example, 100g, and the results are shown in table 2 below:
table 2 results of treatment of example 3
In the experimental process, a multi-mode microwave cavity is adopted, and when no additive is added, the phenomenon of uneven heating of the material after the microwave action is shown in the phenomenon that one section of the material is dry, the oil content is low, and the other section of the material is wet. When the activated carbon or the additive b is added, the heating effect is better because most of the oil and the water are removed. And the deoiling rate after the additive b is added is slightly higher than that when the same weight of the activated carbon is added, but as in example 1, the sample mixed with the activated carbon is also heated unevenly in the microwave treatment process, and the cylindrical reactor is damaged after multiple treatments. The microwave distribution of the additive b is more uniform, and the phenomenon of nonuniform heating can not occur, which shows that no vitrification of the sample or damage of the reactor can be found after multiple reactions.
In addition, comparing the treatment results of example 1 and example 2, it is found that the additive b is much more effective than the activated carbon in treating the solid waste containing heavy oil, and the additive b has a wider application range than the activated carbon and a better application prospect. Of course, it will be understood by those skilled in the art that although examples 1 and 2 illustrate only additive b, other additives consistent with the objects of the present invention still have better treatment effects than activated carbon when treating oil-heavy solid waste.
Example 4
The method is characterized in that oil-containing drilling waste is taken as a treatment object, the oil content of the oil-containing drilling waste is 21.8%, the water content of the oil-containing drilling waste is 5.1%, microwave treatment is carried out in a cylindrical reactor of a multi-mode resonant cavity, when microwaves with the power of 5kW and the frequency of 2450MHz are used for treating a sample for 30s, the deoiling rate of the sample is 65.60%.
When 5% by weight of activated carbon was added and mixed uniformly with the sample, the sample was treated with microwaves of the same power and frequency for 30 seconds, and the deoiling ratio of the sample was 94.45%.
When 5% by weight of additive a consisting of 75% of phenolic resin, 5% of titanium oxide, 18% of boron oxide and 2% of aluminum oxide is added, and the mixture is uniformly mixed with the sample and then heated for 30s, the deoiling rate can reach 94.04%.
When 5% by weight of additive b consisting of 75% mannan and 25% titanium oxide was added, and the mixture was uniformly mixed with the sample and heated for 30 seconds, the deoiling rate was 97.11%.
When 5% by weight of additive c consisting of 25% cellulose and 75% sodium phosphate is added, and the mixture is uniformly mixed with the sample and then heated for 30s, the deoiling rate can reach 97.71%.
When 5% of additive d consisting of 25% of phenolic resin, 25% of epoxy resin, 25% of starch and 25% of alumina is added, and is uniformly mixed with the sample, the mixture is heated for 30s, and the deoiling rate can reach 94.95%.
When 5% by weight of additive e consisting of 25% of epoxy resin, 25% of glucan, 20% of silicon oxide, 10% of iron oxide, 10% of sodium phosphate and 10% of sodium silicate is added, and is uniformly mixed with the sample, the mixture is heated for 30s, and the deoiling rate can reach 97.25%.
When 5% by weight of additive f consisting of 1% of glucan, 30% of titanium oxide and 69% of calcium oxide is added, and the mixture is uniformly mixed with the sample and then heated for 30s, the deoiling rate can reach 97.71%.
When 5% by weight of additive g consisting of 75% of phenolic resin, 24% of glucan and 1% of silicon oxide is added, and the mixture is uniformly mixed with the sample and then heated for 30s, the deoiling rate can reach 95.87%.
When 5% of additive h consisting of 50% of glucan, 30% of titanium oxide and 20% of magnesium oxide is added, and the mixture is uniformly mixed with the sample and then heated for 30s, the deoiling rate can reach 96.79%.
In this embodiment, the weight of the mixture may be, for example, 100g, and the processing results are shown in table 3 below:
table 3 results of treatment of example 4
As can be seen from the above table, when the additive a to the additive h are mixed in the oil-containing drilling waste, the deoiling rate of the sample is higher than that of the sample without the additive when the sample is treated by using the microwave with the power of 5KW and the frequency of 2450 MHz; although the deoiling rate of the additive a is slightly lower than that of the activated carbon with the same weight, the samples added with the additives a to h do not have the problem of uneven heating.
Example 5
The method comprises the steps of taking oil-containing drilling waste as a treatment object, wherein the oil content of the oil-containing drilling waste is 21.8%, the water content of the oil-containing drilling waste is 5.1%, the oil-containing drilling waste is uniformly mixed with an additive a, then the mixture is sent into a cylindrical reactor of a multi-mode resonant cavity to be subjected to microwave treatment, wherein the composition of the additive a is 75% of phenolic resin, 5% of titanium oxide, 18% of boron oxide and 2% of aluminum oxide, the weight of the additive a is 1% -35% of the weight of a mixture of the oil-containing drilling waste and the additive a, and the weight of the mixture can be 100g, for example. When heating was carried out using microwaves with a power of 5KW and a frequency of 2450MHZ, the treatment results are shown in table 4 below:
table 4 results of treatment of example 5
As can be seen from the above table, when the additive amount of the additive a is gradually increased, the deoiling rate is rapidly increased, and when the additive amount of the additive a is 15% by weight, the deoiling rate is maximized, and then when the additive amount is continuously increased, the time required for the sample to be subjected to microwave heating is shortened under the condition that the same deoiling rate is achieved, so that the energy consumption required for processing the sample is reduced, in other words, the energy consumption required by each kilogram of the samples is reduced (see the last column in table 4), so that the energy utilization rate is improved, and the environmental protection and the high efficiency are achieved.
Example 6
The method comprises the steps of taking crude oil waste as a treatment object, wherein the oil content of the crude oil waste is 25.0%, the water content of the crude oil waste is 15.3%, the crude oil waste and an additive b are uniformly mixed and then are sent into a cylindrical reactor of a multi-mode resonant cavity to be subjected to microwave treatment, wherein the additive b comprises 75% of mannan and 25% of titanium oxide, the weight of the additive b is 1% -35% of the weight of a mixture of the crude oil waste and the additive b, and the weight of the mixture can be 100g, for example. When heating was carried out using microwaves with a power of 3KW and a frequency of 2450MHZ, the treatment results are shown in table 5 below:
table 5 results of treatment of example 6
As can be seen from the above table, when the additive amount of the additive b is gradually increased, the deoiling rate is rapidly increased and the required treatment time is also significantly reduced, and when the additive amount of the additive b is 15% by weight, the deoiling rate is maximized and only 30 seconds of treatment are required; and when the addition amount is continuously increased, the time for the sample to be heated by the microwave is further shortened under the condition of reaching the same deoiling rate, so that the energy consumption for treating the sample is reduced, and the environment-friendly effect is better.
It can be seen from examples 2 and 6 that when 5% by weight of additive b was added simultaneously, the oil removal rate of the mono-mode cavity was significantly higher than that of the multi-mode cavity, and the heating time was shorter and the process efficiency was higher.
Further, it is understood from examples 5 and 6 that when the additive a and the additive b are added in an amount of 5% to 30%, good oil removing effect can be obtained, and particularly when the additive is added in an amount of 5% to 15%, good oil removing rate can be obtained. When the addition amount of the additive a and the additive b is increased from 15% to 35%, the deoiling ratio is basically not changed, but the treatment time can be greatly shortened, so that the method is very suitable for a continuous production process. Of course, it will be understood by those skilled in the art that although examples 5 and 6 illustrate the effect of additive a and additive b on the oil removal rate and treatment time, other additives which meet the objectives of the present invention will still meet the above criteria.
In addition, although the technical solutions of the present invention are described in detail in the above examples, it should be understood by those skilled in the art that any technical features, examples and embodiments in the above examples can be combined or simply replaced, for example, the solution of using only starch or epoxy resin for the high molecular polymer and only potassium phosphate or sodium silicate for the inorganic salt is still within the protection scope of the present invention, as long as the object of the present invention is not violated.
Claims (6)
1. An additive for treating oily solid waste, which comprises the following components in percentage by weight:
1 to 99 percent of high molecular polymer and 1 to 99 percent of solid inorganic matter;
the additive is used for enabling microwave heating to be uniform during microwave heating;
wherein the inorganic substance is one or more of inorganic salt and salified oxide;
the salified oxide is one or more of a basic oxide, an acidic oxide and an amphoteric oxide;
the alkaline oxide is one or more of ferric oxide, calcium oxide and magnesium oxide;
the acidic oxide is one or more of silicon oxide and boron oxide;
the amphoteric oxide is one or more of aluminum oxide and titanium oxide.
2. The additive according to claim 1, wherein the high molecular polymer is one or more of a polysaccharide high molecular polymer, an epoxy resin and a phenol resin.
3. The additive according to claim 2, wherein the polysaccharide high molecular polymer is one or more of dextran, mannan, starch and cellulose.
4. The additive of claim 1, wherein the inorganic salt is one or more of a silicate and a phosphate.
5. A method of treating oil-containing solid waste, comprising:
uniformly mixing the additive and the oily solid waste according to any one of claims 1 to 4, wherein the weight of the additive is 1 to 35 percent of the weight of the mixture of the additive and the oily solid waste;
and putting the mixed materials into a resonant cavity of microwave equipment, and heating by using microwaves.
6. The method of claim 5, wherein the weight of the additive is 5% to 30% of the weight of the mixture.
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