CN105462603A - Method for preparing fuel oil through liquid-solid co-catalytic cracking of waste plastics, rubbers and waste engine oil - Google Patents
Method for preparing fuel oil through liquid-solid co-catalytic cracking of waste plastics, rubbers and waste engine oil Download PDFInfo
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- CN105462603A CN105462603A CN201410389469.9A CN201410389469A CN105462603A CN 105462603 A CN105462603 A CN 105462603A CN 201410389469 A CN201410389469 A CN 201410389469A CN 105462603 A CN105462603 A CN 105462603A
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Abstract
The present invention discloses a method for preparing fuel oil through liquid-solid co-catalytic cracking of waste plastics, rubbers and waste engine oil. According to the method, waste plastics and waste rubbers are added to a cracking reactor, heating is performed under a pressure reducing condition to carry out a cracking reaction, waste engine oil and a catalyst are mixed in the waste rubbers, and the used catalyst comprises tricalcium silicate, dicalcium silicate, tricalcium aluminate, tetracalcium aluminoferrite, calcium oxide, calcium carbonate, sodium oxide and potassium oxide. The method of the present invention has characteristics of low energy consumption, cracking reaction rate improving, cracking temperature reducing, cracking oil recovery rate improving, and high-quality oil product obtaining.
Description
Technical field
The invention belongs to field of Environment Protection, be specifically related to a kind ofly produce the method for oil fuel with plastic waste, the liquid-solid catalytic pyrolysis altogether of rubber, used oil.
Background technology
Waste rubber, plastic waste are difficult to natural degradation under normal circumstances, and " white pollution " problem also becomes more and more serious.Utilize waste rubber, cracking waste plastics produces the mode that fuel oil is a kind of regeneration.Current employing, by after waste rubber, plastic waste fragmentation, is put into scission reaction still and is carried out scission reaction, the gas phase mixture matter that obtains together with catalyzer, passing through condensation heat sink, carry out cooling process, and then carry out oily-water seperating equipment, and obtain thick oil, waste water and combustion gas.Equipment used is general-purpose equipment, as horizontal or vertical scission reaction still, condensation heat sink, oil-water-gas separating device etc.The catalyzer that general use crack crude technique is used, as HY, Ni-REY, HZSM mono-5 equimolecular sieve catalyst, because the catalytic reforming of cracking waste plastics product and crack crude product has similarity.But oil composition comparatively plastic waste is much complicated, thus with the modified catalyst catalysis cracking waste plastics gas of crack crude can produce ox such as poisoning of catalyst, reaction not thoroughly, the low and difficult life of catalyzer of lysis efficiency, high in cost of production variety of problems.
Summary of the invention
The object of the invention is for prior art Problems existing, there is provided a kind of and produce the method for oil fuel with plastic waste, rubber, the liquid-solid catalytic pyrolysis altogether of used oil, the method not only consumes energy low, also has high heating rate and yield, and can obtain high-quality oil product.
The method producing oil fuel with plastic waste, rubber, the liquid-solid catalytic pyrolysis altogether of used oil provided by the invention is that plastic waste, waste old are added cracking reactor, scission reaction is carried out in heating at reduced pressure conditions, used oil and catalyzer has also been mixed in waste old, the blending ratio of plastic waste, waste old, waste lubricating oil and catalyzer counts l:0.1 ~ 5:0.0001 ~ 5 by weight, cracking pressure is 30 ~ 750 mmhg, scission reaction temperature 300-500 DEG C, preferred 300-450 DEG C, the scission reaction time is 0.1-20 minutes.
Used oil used in aforesaid method is at least one in waste hydraulic oil, useless gear oil, waste oils from compressor, waste electric appliance transformer oil, used heat conduction oil.
Catalyzer used in aforesaid method comprises tricalcium silicate, Dicalcium Phosphate (Feed Grade), tricalcium aluminate, tetracalcium aluminoferrite, calcium oxide, calcium carbonate, sodium oxide, potassium oxide, wherein said catalyzer is by weight by tricalcium silicate 30 1 60, Dicalcium Phosphate (Feed Grade) l5-37, tricalcium aluminate 7 one l5, tetracalcium aluminoferrite l0-18, calcium oxide 20-30, calcium carbonate l0 mono-l5, sodium oxide 2-5, potassium oxide 1-3, is crushed to 200 orders mixes after mixing through ball mill pulverizer;
Cracking reactor used in aforesaid method is conventional chemical reactor, as tank reactor or fixed-bed reactor or fluidized-bed reactor.
The gas generated by aforesaid method reaction cracking, at the neutralizing tower that unslaked lime is housed through, after eliminating the corrosive gasess such as wherein contained H2S, then by condenser condenses, is separated into non-condensable gases and cracked oil.Non-condensable gases is mainly low molecular hydrocarbon material, can directly use as fuel.The cracked oil obtained, by known chemical separating method, can obtain various important Organic chemical products further, and wherein remaining heavy cracked oil can reenter in cracking reactor and participate in scission reaction.The residue that reaction cracking generates obtains carbon black by known method.Steel wire also can melt down smelting.
The present invention compared with prior art, has the following advantages:
1, because the inventive method adds waste lubricating oil in reaction system, thus improve the homogeneity of cracking system on the one hand, increase heat and mass speed, also promote the carrying out of catalytic cracking reaction on the other hand, improve yield and the quality of cracked oil.
2, because the inventive method adds catalyzer in reaction system simultaneously, thus improve scission reaction speed (0.1-20 minutes) on the one hand, also reduce cracking temperature (300 DEG C can be low to moderate) on the other hand simultaneously and the energy consumption of scission reaction is greatly reduced.
3, the oil yield of cracking not only greatly can be improved by the inventive method, make it to reach 40-60%, but also light oil content in cracked oil is increased, reach 25-40%, also substantially increase the quality of oil product in addition, make the content of polycyclic aromatic hydrocarbons in oil product be reduced to 10-20%, mononuclear aromatics has brought up to 30-40%, the content of terpadiene has brought up to l5-30%, adds the economic worth of oil product.
4, conveniently by the chemical separating method separating-purifying of some routines, various important Organic chemical products can be obtained with the split product that the inventive method obtains.
5, can directly process the one piece tyre with comparatively large vol by the inventive method, thus save and pulverize and be separated the expenses such as steel wire, reduce processing cost.
Embodiment
Below by embodiment, the present invention will be further described:
EXAMPLE l:
Junked tire, useless vacuum pump oil, NaZSM.5 with the ratio of 1:l:O.1, are joined in cracking reactor and mixed by weight, and " C carries out scission reaction 5 minutes under 30mmH9 pressure, to be warming up to 300.The gas that reaction cracking generates is at the neutralizing tower that unslaked lime is housed through, after eliminating the corrosive gasess such as wherein contained H2S, pass through condenser condenses again, be separated into non-condensable gases and cracked oil, the cracked oil yield obtained is 50.6%, and in cracked oil, polycyclic aromatic hydrocarbons, mononuclear aromatics and terpadiene content are as shown in table l.Non-condensable gases is mainly low molecular hydrocarbon material, can directly use as fuel; The cracked oil obtained passes through gas-chromatography. mass spectroscopy component concentration and distribution, and extract different fractions through distillation operation, the light oil content wherein extracted accounts for 35.1% of total cracked oil quality; Wherein heavy cracked oil can be used as waste lubricating oil and reenters in reactor and participate in new scission reaction.The residue that reaction cracking generates obtains carbon black by known method.Steel wire also can melt down smelting.
Embodiment 2
Junked tire, Waste gasoline machine oil, USY with the ratio of 1:1.5:O.5, are joined in cracking reactor and mixed by weight, and " C carries out scission reaction 6 seconds under 100mmH9 pressure, to be warming up to 500.The gas that reaction cracking generates is at the neutralizing tower that unslaked lime is housed through, after eliminating the corrosive gasess such as wherein contained H2S, pass through condenser condenses again, be separated into non-condensable gases and cracked oil, the cracked oil yield obtained is 50.2%, and in cracked oil, polycyclic aromatic hydrocarbons, mononuclear aromatics and terpadiene content are as shown in table 1.Non-condensable gases is mainly low molecular hydrocarbon material, can directly use as fuel: the cracked oil obtained passes through gas-chromatography. mass spectroscopy component concentration and distribution, and extracting different fractions through distillation operation, the light oil content wherein extracted accounts for the 32-3% of total cracked oil quality; Wherein heavy cracked oil can be used as waste lubricating oil and reenters in reactor and participate in new scission reaction.The residue that reaction cracking generates obtains carbon black by known method.Steel wire also can melt down smelting.
Embodiment 3
Junked tire, waste diesel machine oil, MCM-41 with the ratio of 1:3:3, are joined in cracking reactor and mix by weight, under 200mmH9 pressure, is warming up to 450.C carries out scission reaction 30 seconds.The gas that reaction cracking generates is at the neutralizing tower that unslaked lime is housed through, after eliminating the corrosive gasess such as wherein contained HzS, pass through condenser condenses again, be separated into non-condensable gases and cracked oil, the cracked oil yield obtained is 60.1%, and in cracked oil, polycyclic aromatic hydrocarbons, mononuclear aromatics and terpadiene content are as shown in table 1.Non-condensable gases is mainly low molecular hydrocarbon material, can directly use as fuel; The cracked oil obtained passes through gas-chromatography. mass spectroscopy component concentration and distribution, and extract different fractions through distillation operation, the light oil content wherein extracted accounts for 25.6% of total cracked oil quality; Wherein heavy cracked oil can be used as waste lubricating oil and reenters in reactor and participate in new scission reaction.The residue that reaction cracking generates obtains carbon black by known method.Steel wire also can melt down smelting.
Embodiment 4
Junked tire, useless gear oil, waste diesel machine oil, cross-linked montmorillonite with the ratio of 1-1:l:1, are joined in cracking reactor and are mixed, under 300mmH9 pressure, is warming up to 350 " CJ difference row scission reaction 3 minutes by weight.The gas that reaction cracking generates is at the neutralizing tower that unslaked lime is housed through, after eliminating the corrosive gasess such as wherein contained H2S, pass through condenser condenses again, be separated into non-condensable gases and cracked oil, the cracked oil yield obtained is 56.1%, and in cracked oil, polycyclic aromatic hydrocarbons, mononuclear aromatics and terpadiene content are as shown in table 1.Non-condensable gases is mainly low molecular hydrocarbon material, can directly use as fuel; The cracked oil obtained passes through gas-chromatography. mass spectroscopy component concentration and distribution, and extracting different fractions through distillation operation, the light oil content wherein extracted accounts for 30.8% of total cracked oil quality: wherein heavy cracked oil can be used as waste lubricating oil and reenters in reactor and participate in new scission reaction.The residue that reaction cracking generates obtains carbon black by known method.Steel wire also can melt down smelting.
Embodiment 5
By junked tire, waste hydraulic oil, silicon aluminium microsphere by weight with the ratio of l:3:1, join in cracking reactor and mix, under 500mmH9 pressure, be warming up to 450.C carries out scission reaction 2 minutes.The gas that reaction cracking generates is at the neutralizing tower that unslaked lime is housed through, after eliminating the corrosive gasess such as wherein contained H2S, pass through condenser condenses again, be separated into non-condensable gases and cracked oil, the cracked oil yield obtained is 43.8%, and in cracked oil, polycyclic aromatic hydrocarbons, mononuclear aromatics and terpadiene content are as shown in table l.Non-condensable gases is mainly low molecular hydrocarbon material, can directly use as fuel; The cracked oil obtained passes through gas-chromatography. mass spectroscopy component concentration and distribution, and extracting different fractions through distillation operation, the light oil content wherein extracted accounts for 34.6% of total cracked oil quality: wherein heavy cracked oil can be used as waste lubricating oil and reenters in reactor and participate in new scission reaction.The residue that reaction cracking generates obtains carbon black by known method.Steel wire also can melt down smelting.
Embodiment 6
Junked tire, useless transformer oil, REY with the ratio of 1:0.5:0.001, are joined in cracking reactor and mix by weight, under 750mmH9 pressure, is warming up to 400.C carries out scission reaction 20 minutes.The gas that reaction cracking generates is at the neutralizing tower that unslaked lime is housed through, after eliminating the corrosive gasess such as wherein contained H2S, pass through condenser condenses again, be separated into non-condensable gases and cracked oil, the cracked oil yield obtained is 52.3%, and in cracked oil, polycyclic aromatic hydrocarbons, mononuclear aromatics and terpadiene content are as shown in table 1.Non-condensable gases is mainly low molecular hydrocarbon material, can directly use as fuel: the cracked oil obtained passes through gas-chromatography. mass spectroscopy component concentration and distribution,
And extracting different fractions through distillation operation, the light oil content wherein extracted accounts for 38.5% of total cracked oil quality: wherein heavy cracked oil can be used as waste lubricating oil and reenters in reactor and participate in new scission reaction.The residue that reaction cracking generates obtains carbon black by known method.Steel wire also can melt down smelting.
Embodiment 7
Junked tire, useless thermal oil, using natural clinoptilolite, NaZSM.5 with the ratio of 1:5:4.999:0.001, are joined in cracking reactor and mix by weight, under 40mmH9 pressure, is warming up to 320.C carries out scission reaction 15 minutes.The gas that reaction cracking generates is at the neutralizing tower that unslaked lime is housed through, after eliminating the corrosive gasess such as wherein contained H2S, pass through condenser condenses again, be separated into non-condensable gases and cracked oil, the cracked oil yield obtained is 58.6%, and in cracked oil, polycyclic aromatic hydrocarbons, mononuclear aromatics and terpadiene content are as shown in table 1.Non-condensable gases is mainly low molecular hydrocarbon material, can directly use as fuel; The cracked oil obtained passes through gas-chromatography. mass spectroscopy component concentration and distribution, and extract different fractions through distillation operation, the light oil content wherein extracted accounts for 27.5% of total cracked oil quality; Wherein heavy cracked oil can be used as waste lubricating oil and reenters in reactor and participate in new scission reaction.The residue that reaction cracking generates obtains carbon black by known method.Steel wire also can melt down smelting.
Embodiment 8
Junked tire, waste steam turbine oil, DeLaZSM.5 with the ratio of 1:0.1:0.0001, are joined in cracking reactor and mix by weight, under 400mmH9 pressure, is warming up to 450.C carries out scission reaction l0 minute.The gas that reaction cracking generates is at the neutralizing tower that unslaked lime is housed through, after eliminating the corrosive gasess such as wherein contained H:s, pass through condenser condenses again, be separated into non-condensable gases and cracked oil, the cracked oil yield obtained is 52.5%, and in cracked oil, polycyclic aromatic hydrocarbons, mononuclear aromatics and terpadiene content are as shown in Table I.Non-condensable gases is mainly low molecular hydrocarbon material, can directly use as fuel; The cracked oil obtained analyzes component concentration and distribution by gas chromatography and mass spectromentry, and extracts different fractions through distillation operation, and the light oil content wherein extracted accounts for the 40.o% of total cracked oil quality; Wherein heavy cracked oil can be used as waste lubricating oil and reenters in reactor and participate in new scission reaction.The residue that reaction cracking generates obtains carbon black by known method.Steel wire also can melt down smelting.
More than to invention has been exemplary description; obvious realization of the present invention is not subject to the restrictions described above; as long as have employed the various improvement that technical solution of the present invention is carried out; or design of the present invention and technical scheme directly applied to other occasion, all in protection scope of the present invention without to improve.
Claims (3)
1. produce the method for oil fuel with plastic waste, waste rubber, the liquid-solid catalytic pyrolysis altogether of used oil for one kind, it is characterized in that, plastic waste, waste rubber are added cracking reactor, scission reaction is carried out in heating at reduced pressure conditions, in plastic waste, waste rubber, be mixed with used oil and catalyzer simultaneously, the blending ratio of plastic waste, waste old, waste lubricating oil and catalyzer counts l:0.1 ~ 5:0.0001 ~ 5 by weight, cracking pressure is 30 ~ 750 mmhg, scission reaction temperature 300-500 DEG C, preferred 300-450 DEG C, the scission reaction time is 0.1-20 minutes.
2. according to claim 1ly a kind ofly produce the method for oil fuel with plastic waste, the liquid-solid catalytic pyrolysis altogether of waste rubber, used oil, it is characterized in that, described catalyzer comprises tricalcium silicate, Dicalcium Phosphate (Feed Grade), tricalcium aluminate, tetracalcium aluminoferrite, calcium oxide, calcium carbonate, sodium oxide, potassium oxide; Described catalyzer is by weight by tricalcium silicate 30 1 60, Dicalcium Phosphate (Feed Grade) l5-37, tricalcium aluminate 7 one l5, tetracalcium aluminoferrite l0-18, calcium oxide 20-30, calcium carbonate l0 mono-l5, sodium oxide 2-5, potassium oxide 1-3, is crushed to 200 orders mixes after mixing through ball mill pulverizer.
3. according to claim 1ly a kind ofly produce the method for oil fuel with plastic waste, the liquid-solid catalytic pyrolysis altogether of waste rubber, used oil, it is characterized in that cracking reactor used in aforesaid method is conventional chemical reactor, as tank reactor or fixed-bed reactor or fluidized-bed reactor.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106423296A (en) * | 2016-08-28 | 2017-02-22 | 山东成泰化工有限公司 | Silicon rubber catalyst composition |
| CN108531208A (en) * | 2018-04-09 | 2018-09-14 | 青岛科技大学 | A method of drawing off agent catalytic pyrolysis high-molecular compound using FCC |
| CN114570400A (en) * | 2022-03-20 | 2022-06-03 | 胡进 | Catalyst for reducing oil-wax ratio in organic solid waste thermal cracking process, catalyst structural member and application |
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2014
- 2014-08-08 CN CN201410389469.9A patent/CN105462603A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106423296A (en) * | 2016-08-28 | 2017-02-22 | 山东成泰化工有限公司 | Silicon rubber catalyst composition |
| CN108531208A (en) * | 2018-04-09 | 2018-09-14 | 青岛科技大学 | A method of drawing off agent catalytic pyrolysis high-molecular compound using FCC |
| CN114570400A (en) * | 2022-03-20 | 2022-06-03 | 胡进 | Catalyst for reducing oil-wax ratio in organic solid waste thermal cracking process, catalyst structural member and application |
| CN114570400B (en) * | 2022-03-20 | 2024-03-26 | 胡进 | catalyst for reducing oil-wax ratio in organic solid waste heat pyrolysis process, catalyst structural member and application |
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Application publication date: 20160406 |