CN101491726B - Dioxins inhibitor and manufacturing method thereof - Google Patents
Dioxins inhibitor and manufacturing method thereof Download PDFInfo
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- CN101491726B CN101491726B CN 200810003583 CN200810003583A CN101491726B CN 101491726 B CN101491726 B CN 101491726B CN 200810003583 CN200810003583 CN 200810003583 CN 200810003583 A CN200810003583 A CN 200810003583A CN 101491726 B CN101491726 B CN 101491726B
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- oxide
- inhibitor
- iron
- calcium
- dioxins
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Abstract
The invention discloses a dioxin inhibitor, which is prepared from rubber pyrolysis oil and a metallic oxide, wherein the rubber pyrolysis oil is produced through the thermal cracking of tires and contains 0.5 to 1.5 percent of sulfur, and the metallic oxide is an oxide of iron, an oxide of calcium or a mixture of the oxide of iron and the oxide of calcium. Taking the weight of the inhibitor in a dry state as a reference, the inhibitor comprises 1 to 5 weight percent of sulfur, 10 to 35 weight percent of iron and 0.5 to 1.5 weight percent of calcium.
Description
Technical field
The present invention relates to a kind of dioxins inhibitor, relate in particular to a kind of by prepared dioxins inhibitor and the manufacture method thereof of rubber cracking oil.
Background technology
Along with the progress in epoch, relative, the air-polluting problem is day by day serious, and national governments there's no one who doesn't or isn't rack one's brains and make every effort to improve, and along with the increasingly stringent of environmental requirement, industrial quarters needs more urgent to effective control air-polluting.
As everyone knows, harmful material in the general air pollution probably can be divided into volatile organic solvent (VOC) discarded object, nitrogen oxide (NOx) and dioxin (Dioxin) etc.
Wherein, because dioxin has anxious toxicity to organism, and can constantly accumulate in body, " poison in century " is otherwise known as.Dioxin mainly is to be present in urban waste, trade waste or the Biohazard Waste that contains the chlorine polymer, in incineration course, although under high-temperature operation, the burning product dioxin of rubbish or discarded object can be decomposed, but also may have part dioxin residue, or the dioxin that in temperature-fall period, had originally decomposed again polymerization form dioxin.
Please refer to Fig. 1, it is the formation mechanism schematic diagram of known dioxin.Wherein, as shown in the figure, discarded object 1 may produce straight chain hydrocarbon compound 20 and aromatic hydrocarbons 21 in the process of combustion reaction S101, also may also residually part unburned carbon 22 be arranged or directly generate dioxin 3.Then, straight chain hydrocarbon compound 20, aromatic hydrocarbons 21 and unburned carbon 22 can be respectively via cyclization S102, aminating reaction S103 and low temperature again synthetic reaction S104 form the aromatic hydrocarbons 23 of ammonification that is dioxin precursor 23.In addition, unburned carbon 22 also can via low temperature again synthetic reaction S104 directly generate dioxin 3.At last, the aromatic compound 23 of ammonification (being the dioxin precursor) forms dioxin 3 via the incorgruous catalytic reaction S106 of predecessor.
According to the formation mechanism of above-mentioned dioxin 3 can find in incineration course to produce dioxin dominant mechanism nothing more than High Temperature Gas be combined to, predecessor heterogeneous catalytic reaction and low temperature is synthetic again.The generation that therefore will reduce dioxin can stop the generation of its precursor and the dioxin that (2) removal has generated to be set about from (1).
Early stage employed processing method is exactly to utilize the adsorption capacity absorption dioxin of active carbon, and the method for use (active carbon adsorption) has basically: (1) ADSORPTION IN A FIXED BED method (Fixed-bed Filters); (2) active carbon insufflation (Carbon Injection) dual mode, when adopting the active carbon insufflation, the dry type shot-like particle collecting devices such as whirlwind dust collector, bag filter precipitron or electrostatic precipitation machine of must arranging in pairs or groups; If the shot-like particle dust collect plant of incinerator is wet type processing device, adopt the active carbon insufflation, will cause the packed layer of wet scrubber tower or the obstruction of demister (De-mister), and affect the normal operating of incineration system.In addition, the shortcoming of active carbon adsorption is only the dioxin in the gas phase to be transferred in the active carbon, and can't really decompose the destruction dioxin.Therefore, if do not deal carefully with the active carbon that contains dioxin, for example bury waste active carbon after, also might be via the leakage of soaking of underground water, via getting back to after the plant absorbing on the food chain, the final or quilt mankind absorb and the human health of impact, environment are also had the danger of the secondary pollution of causing again.Moreover at present the active carbon price is increasingly expensive, and the practitioner reduces use amount in order to save cost as far as possible, remote-effects check the effect of incinerator discharging dioxin amount.
As for other processing method, such as: catalyst oxidizing process and the thermal decomposition method etc. of burning again, have too the treatment system costliness, do not meet financial cost, maybe need expend the shortcomings such as mass energy.
In sum, at present knownly variously prevent and treat method and fail to reach desirable condition, remain disadvantages, as: the dioxin treatment effect is not good, the required fund of updating the equipment is huge, process with the raw material costliness etc., all waits to improve.Taiwan, Japan build a large amount of incinerators in order to process discarded object now, and the dioxin total amount of discharging every day is quite surprising, so in order to take into account simultaneously above-mentioned all considerations, how to improve existing dioxin control technology and face very acid test.
In view of this, in order effectively to address the above problem, the inventor urgently thinks the method that suppresses or get rid of dioxin in improving invariably, beyond expectation can be found a kind of dioxin inhibition method of saving the raw material cost, also must meet the now requirement of environmental protection new regulation.
Because " environmental protection " is the emphasis of global evolution already, the new concept of discarded object being regarded as resource is not only introduced in Taiwan in recent years, has more formulated the relevant laws and regulations order take environmental protection Basic Law relevant regulations as the basis.
Wherein, fast development along with auto industry and highway transportation industry, all over the world the demand of various tires also increased day by day, the year sales volume of world's tire reaches tens00000000 at present, and each automotive average travels 30,000 to 50,000 kilometers just must change a tire, causes the situation of tire year learies in the world's up to 10,000,000 tons.Therefore, the comprehensive utilization of old tire more and more receives people's concern because this be environmental contamination reduction, the effective way that turns waste into wealth.
Summary of the invention
For solving the problems of the technologies described above, main purpose of the present invention is to provide a kind of dioxins inhibitor (Dioxin inhibitor) that is formed by rubber cracking oil and metal oxide modulation, in the inhibitor that obtains the generation of establishment dioxin, realize the recycling to rubber such as waste tires.
The present invention also aims to provide the preparation method of above-mentioned dioxins inhibitor, obtain rubber cracking oil by waste tire being carried out thermal cracking, and mix the metal oxide acquisition dioxins inhibitor good to the dioxin inhibition.
For achieving the above object, the invention provides a kind of dioxins inhibitor, it is to form with rubber cracking oil and metal oxide modulation.
According to concrete scheme of the present invention, described rubber cracking oil can be (namely this rubber cracking oil is tire pyrolysis oil) of utilizing the hot cracked reaction of the damaged tire that reclaims to generate, and contains the sulphur of 0.5% to 1.5% weight.Described metal oxide can be the oxide of iron, oxide or its mixing of calcium, the mixing of one or more in its optional autoxidation ferrous iron, di-iron trioxide, tri-iron tetroxide, calcium oxide and the calper calcium peroxide etc.
In the dioxins inhibitor provided by the invention, described metal oxide can be selected the oxide from iron, oxide or its mixing of calcium.In addition, take the weight of this inhibitor when the drying regime as benchmark, wherein can comprise the sulphur of 1 to 5 percentage by weight, the iron of 10 to 35 percentage by weights and the calcium of 0.5 to 1.5 percentage by weight.Although the content of described sulphur, iron and calcium is in constituent content, their existence or interpolations in inhibitor are not restricted to simple substance.
The present invention also provides the manufacture method of above-mentioned dioxins inhibitor, and its step comprises: rubber is carried out heat scission reaction to produce rubber cracking oil; And, mix at least a metal oxide to cracked oil, mix forming inhibitor.
According to concrete technical scheme of the present invention, in the manufacture method of dioxins inhibitor, the rubber cracking oil that adopts is by carrying out the heat scission reaction preparation to tire; This rubber cracking oil can contain the sulphur of 0.5% to 1.5% weight.The metal oxide that adopts can be the oxide of iron, oxide or its mixing of calcium, the mixing of one or more in its optional autoxidation ferrous iron, di-iron trioxide, tri-iron tetroxide, calcium oxide and the calper calcium peroxide etc.
In the manufacture process of inhibitor, mix metal oxide to the rubber cracking oil the time, make the mixed ratio of sulphur, iron and calcium be respectively 1 to 5 percentage by weight, 10 to 35 percentage by weights and 0.5 to 1.5 percentage by weight of described inhibitor weight when drying regime.
Dioxins inhibitor provided by the invention; its raw material sources---cracked oil; can use bulk deposition and easily cause the waste tire of environmental pollution, thereby realize resource, the harmless treatment of waste tire, meet concept and the specification requirement of now environmental protection and sustainable development fully.
The use of dioxins inhibitor provided by the invention does not need expensive treating apparatus, can reduce known use catalyst oxidizing process and the thermal decomposition method of burning is again taken high financial cost and huge energy consumption problem processing on the dioxin.
Cracked oil of the present invention is the higher rubber cracking oil of sulfur content, only needs a small amount of cracked oil can modulate inhibitor, has reached cost-effective purpose.And when dioxins inhibitor of the present invention was sprayed on the chlorine-containing waste of wish burning, its consumption only was 0.001 to 0.1 of waste-material dry basic weight amount, therefore, only need provide a small amount of dioxins inhibitor just can effectively suppress the generation of dioxin.
Comprehensive the above, dioxins inhibitor provided by the present invention can not only suppress the generation of dioxin effectively, and enforcement of the present invention has further realized resource, the harmless treatment of waste tire.
Description of drawings
Fig. 1 is the schematic diagram of known dioxin formation mechanism;
Fig. 2 utilizes inhibitor of the present invention to realize suppressing the chemical equation that dioxin generates;
Fig. 3 is the schematic flow sheet of the dioxins inhibitor manufacture method of the embodiment of the invention;
Fig. 4 is the schematic flow sheet of the dioxins inhibitor using method of the embodiment of the invention.
The primary clustering symbol description:
1 discarded object
20 direct steel hydrocarbons
21 aromatic hydrocarbonses
22 unburned carbons
23 ammonification aromatic hydrocarbonses (dioxin precursor)
The 23a chlorobenzene
The 23b chlorophenol
The compound of the 23 ' non-dioxin state
3 dioxins
4 dioxins inhibitors
40 sulphur
41 di-iron trioxides
42 calcium oxide
The accessory substance of 5 dechlorination reactions
S101-S106 dioxin formation mechanism
The S101 combustion reaction
The S102 cyclization
The S103 aminating reaction
S104 low temperature is synthetic reaction again
S105 directly generates
The incorgruous catalytic reaction of S106 predecessor
The manufacturing process of S201-S204 dioxins inhibitor
The use flow process of S301-S303 dioxins inhibitor
The specific embodiment
About the advantages and spirit of the present invention, and more detailed embodiment can be by following embodiment and appended graphic being further understood.
Please refer to Fig. 2, it has shown the chemical equation that utilizes inhibitor of the present invention to realize suppressing the dioxin generation, the discharge capacity of dioxin 3 when incinerating for adopting the generation that stops dioxin precursor (being the ammonification aromatic hydrocarbons) 23 to reduce.
Dioxins inhibitor 4 provided by the present invention is to be formed by rubber cracking oil and metal oxide modulation.Described rubber cracking oil can be to be generated by the hot cracked reaction of the damaged tire that reclaims, and contains 0.5% to 1.5% sulphur 40.And metal oxide is the oxide of iron, oxide or its mixing of calcium, its optional autoxidation ferrous (FeO), di-iron trioxide (Fe
2O
3), tri-iron tetroxide (Fe
3O
4), calcium oxide (CaO) and calper calcium peroxide (CaO
2) etc. in one or more mixing.According to preferred embodiment shown in Figure 2, this metal oxide is di-iron trioxide 41 and the mixture of calcium oxide 42, and this di-iron trioxide 41 is that form with nano level di-iron trioxide exists.
As shown in the figure, when inhibitors 4 is subjected to pyrolytic, will be with SO
xThe chlorine atom that function base displacement dioxin precursor 23 is contained carries out dechlorination reaction (Dechlorination Reaction), forms the compound 23 ' (being the aromatic series sulfur compound) of the lower non-dioxin state of nonpoisonous state or toxicity.Wherein, dioxin precursor 23 can be chlorobenzene (monochlorobenzene, MCB) 23a, chlorophenol (for example 2-chlorophenol (2-monochlorophenol, MCP)) 23b or its mixing.In addition, still accessory substance 5 be can produce after the reaction, iron chloride, calcium chloride and water etc. included.
Then, please refer to Fig. 3, it has shown the schematic flow sheet of manufacture method of the dioxins inhibitor 4 of the embodiment of the invention.As shown in the figure, the manufacture method of a kind of dioxins inhibitor provided by the present invention, its step comprises: at first rubber is carried out heat scission reaction S201, to produce rubber cracking oil S202.Then, mix metal oxide S203 to this rubber cracking oil, and stir to make it fully to mix and form dioxins inhibitor S204.Wherein, described rubber is tire, for example is the discarded tire that reclaims.And metal oxide is di-iron trioxide 41 and the mixing of calcium oxide 42, yet it only is a preferred embodiment, and metal oxide used in the present invention is not limited in this, frontly states clearly.
What further specify is, rubber is carried out the rubber cracking oil of heat scission reaction gained by the present invention, its sulfur content is 0.5% to 1.5% weight, in preferred embodiment, sulfur content is between 0.9%-1.2%, sulfur content compared at present general heavy oil is 0.1%, and rubber cracking oil of the present invention contains higher sulphur composition.
In preferred embodiment, above-mentioned the rubber Pyrolysis be should be the Low Temperature Thermal cracking reaction, wherein the range of reaction temperature of this heat scission reaction is between 300 to 500 ℃.It should be noted that, the cracking technique that general damaged tire recovery is adopted is the Pintsch process with about 1000 ℃, because the organic waste thermal conductance is very low, the discarded object heating must be reached 550 ℃ of-600 ℃ of ability cracking at least and finish, so heat temperature raising is chronic, treating capacity is difficult for enlarging.In addition, because high-temperature process, cracked oil also is easy to vaporization and affects actual oil pump capacity.Process rubber to obtain a large amount of and stable rubber cracking oil so adopt the Low Temperature Thermal cracking reaction in the preferred embodiment of the present invention.Yet this is preferred embodiment of the present invention only, and the present invention is not limited to this, even if react to process rubber also without can not with high temperature pyrolysis.
Moreover what need to specify is, the content of sulphur 40, iron, calcium preferably is respectively 1 to 5 percentage by weight, 10 to 35 percentage by weights and 0.5 to 1.5 percentage by weight with the weighing scale of this inhibitors 4 when the drying regime in the inhibitors 4.
According to above description, just can know composition, proportion of composing and the manufacture method thereof of understanding dioxins inhibitor provided by the invention, and the occupation mode of this dioxins inhibitor can be with further reference to the schematic flow sheet of Fig. 4.
Please refer to Fig. 4, the schematic flow sheet of the dioxins inhibitor using method that it provides for embodiments of the invention.Its using method comprises the following steps: at first, and dioxins inhibitor S301 is provided, and its relevant manufacture method provides in preamble, does not repeat them here.
Then, inhibitor is interspersed among S302 on the chlorine-containing waste of wish burning.Wherein, inhibitor is that the amount in 0.001 to 0.1 ratio of waste-material dry basic weight amount intersperses among on the discarded object, and the mode of its distribution can select blowing to spill, splash or infiltrate, and is not limited to above-mentioned arbitrary mode for it.Subsequently, burning is with the discarded object S303 of inhibitor.Wherein, be that environment at least 800 ℃ or higher temperature carries out combustion reaction with the discarded object of inhibitor, inhibitor institute produce an effect is the most remarkable.Yet this environment for use temperature only is a preferred embodiment, and the environment for use of dioxins inhibitor of the present invention is not limited to this, also can produce the effect that suppresses dioxin.
In sum, can understand that dioxins inhibitor provided by the present invention and manufacture method thereof have following advantages:
(1) dioxins inhibitor among the present invention; its raw material sources---cracked oil; be the waste tire that uses bulk deposition and easily cause environmental pollution, realized resource, the harmless treatment of waste tire, meet concept and the specification requirement of now environmental protection and sustainable development fully.
(2) hold above-mentionedly, just because technical scheme of the present invention is for waste tire recycling, can significantly reduce cost of material.In addition, cracked oil mixed with metal oxide be sprayed on again on the discarded object, the treating apparatus that does not also need costliness also can reduce known use catalyst oxidizing process and the thermal decomposition method of burning is again taken high financial cost and huge energy consumption problem on the processing dioxin.Moreover, compared to known use active carbon adsorption, there is not the problem of follow-up secondary pollution yet, see that really the present invention can effectively solve the problem that faces on the known skill.
(3) more as mentioned before, cracked oil prepared in accordance with the present invention, its sulfur content is 0.5% to 1.5% weight, is the higher cracked oil of sulfur content, meaning namely only needs a small amount of cracked oil can modulate inhibitor, has reached cost-effective purpose.
(4) according to the step S302 of aforementioned using method, when dioxins inhibitor of the present invention is sprayed on the chlorine-containing waste of wish burning, be to intersperse among on the discarded object with respect to discarded object ratio of 0.001 to 0.1 of weight when the drying regime.Therefore, only need provide a small amount of dioxins inhibitor just can effectively suppress the generation of dioxin, relatively also reach cost-effective purpose.
Though the present invention illustrates as above with preferred embodiments, so it is not to limit the present invention's spirit only to terminate in above-described embodiment with the invention entity.The technical staff in the technical field is when understanding easily and utilize other assembly or mode to produce identical effect.Be with, the modification of doing within not breaking away from spirit of the present invention and scope all should be included in the claim scope of the present invention.
Claims (4)
1. dioxins inhibitor, to form with rubber cracking oil and metal oxide modulation, wherein, described rubber cracking oil contains the sulphur of 0.5% to 1.5% weight, described metal oxide is the mixing of the oxide of the oxide of iron and calcium, the oxide of described iron is selected from one or more the mixing in ferrous oxide, di-iron trioxide, the tri-iron tetroxide, and the oxide of described calcium is selected from one or more the mixing in calcium oxide and the calper calcium peroxide; Take the weight of this inhibitor when the drying regime as benchmark, wherein comprise the sulphur of 1 to 5 percentage by weight, the iron of 10 to 35 percentage by weights and the calcium of 0.5 to 1.5 percentage by weight.
2. dioxins inhibitor as claimed in claim 1, wherein, described rubber cracking oil is tire pyrolysis oil.
3. the manufacture method of a dioxins inhibitor, its step comprises:
Rubber is carried out heat scission reaction with preparation rubber cracking oil; And
Mix metal oxide to this rubber cracking oil, mix forming inhibitor;
Wherein, described rubber cracking oil contains the sulphur of 0.5% to 1.5% weight, described metal oxide is the mixing of the oxide of the oxide of iron and calcium, the oxide of described iron is selected from one or more the mixing in ferrous oxide, di-iron trioxide, the tri-iron tetroxide, and the oxide of described calcium is selected from one or more the mixing in calcium oxide and the calper calcium peroxide; Wherein, mix the step of metal oxide to the rubber cracking oil, make the mixed ratio of sulphur, iron and calcium be respectively 1 to 5 percentage by weight, 10 to 35 percentage by weights and 0.5 to 1.5 percentage by weight of described inhibitor weight when drying regime.
4. the manufacture method of dioxins inhibitor as claimed in claim 3, wherein, described rubber cracking oil is by carrying out the heat scission reaction preparation to tire.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810003583 CN101491726B (en) | 2008-01-25 | 2008-01-25 | Dioxins inhibitor and manufacturing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810003583 CN101491726B (en) | 2008-01-25 | 2008-01-25 | Dioxins inhibitor and manufacturing method thereof |
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| CN101491726A CN101491726A (en) | 2009-07-29 |
| CN101491726B true CN101491726B (en) | 2013-02-20 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4745226A (en) * | 1986-09-22 | 1988-05-17 | Stauffer Chemical Company | Reaction of sulfur with polychlorinated polyphenyls |
| CN1031188A (en) * | 1987-08-11 | 1989-02-22 | 米泽化学工业株式会社 | The method for non-pollution processing of halogenated organic compounds |
| TW200402316A (en) * | 2002-08-07 | 2004-02-16 | Miura Kogyo Kk | Soil treatment agent and soil treating method |
| CN1850371A (en) * | 2006-06-02 | 2006-10-25 | 清华大学 | Micro-wave heating desorption/alkyl catalytic decomposition treatment method for polychlorinated biphenyl in soil |
-
2008
- 2008-01-25 CN CN 200810003583 patent/CN101491726B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4745226A (en) * | 1986-09-22 | 1988-05-17 | Stauffer Chemical Company | Reaction of sulfur with polychlorinated polyphenyls |
| CN1031188A (en) * | 1987-08-11 | 1989-02-22 | 米泽化学工业株式会社 | The method for non-pollution processing of halogenated organic compounds |
| TW200402316A (en) * | 2002-08-07 | 2004-02-16 | Miura Kogyo Kk | Soil treatment agent and soil treating method |
| CN1850371A (en) * | 2006-06-02 | 2006-10-25 | 清华大学 | Micro-wave heating desorption/alkyl catalytic decomposition treatment method for polychlorinated biphenyl in soil |
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| CN101491726A (en) | 2009-07-29 |
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