CN102824718B - Compound catalytic dechlorinating agent - Google Patents
Compound catalytic dechlorinating agent Download PDFInfo
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- CN102824718B CN102824718B CN201210330235.8A CN201210330235A CN102824718B CN 102824718 B CN102824718 B CN 102824718B CN 201210330235 A CN201210330235 A CN 201210330235A CN 102824718 B CN102824718 B CN 102824718B
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Abstract
The invention discloses a compound catalytic dechlorinating agent, which consists of the following components in weight percentage: 40-60 percent of combustion improver, 1-5 percent of active agent, 15-20 percent of chelating agent and 30-40 percent of stabilizer, wherein the sum of the components is 100 percent; the combustion improver is one or the composition of more than two of alcohol-based fuels; the active agent consists of the following components in weight percentage: 20-40 percent of nano-ferric oxide, 20-40 percent of nano-ferrous oxide and 20-40 percent of nano-ferroferric oxide; the chelating agent is one or the composition of more than two of high-grade aliphatic amines; and the stabilizer consists of the following components in weight percentage: 20-30 percent of quartz, 20-30 percent of apatite and 40-50 percent of calcium peroxide. By using the compound catalytic dechlorinating agent, organic chloride in chlorine-contained solid waste can be effectively removed, wherein the chlorine-contained solid waste refers to household garbage or organic chloride, such as polyvinyl chloride (PVC), polyvinyl dichloride (PVDC) and the like.
Description
Technical field
The present invention relates to a kind of antichlor, be specifically related to compound catalysis dechlorination agent.
Background technology
In recent years, along with improving constantly of people's living standard, the quantity of house refuse day by day increases.In China, burning method effectively subtracts as a kind of the garbage disposal means holding decrement, obtains increasingly extensive utilization.But live containing some high molecular polymers in rubbish, especially with " white pollution " plastics for representative, therefore house refuse inevitably can produce secondary pollution in burning process, except generating SO
2, SO
x, H
2outside the inorganic matters such as S, HCl, also generate the great hypertoxic organic pollution bioxin of environmental hazard.
Formed from house refuse for bioxin and existing more than 20 year of the research of emission mechanism, but the formation mechanism of bioxin is not studied thoroughly.There are 3 kinds of dominant mechanisms in the discharge source of current generally accepted combustion process Zhong bioxin: 1. itself contain bioxin in fuel and be not destroyed in burning, be present in the flue gas after burning; 2. non-complete combustion of fuel creates some ring-type predecessors (chlorination aromatic hydrocarbon) similar to bioxin structure, and these predecessors pass through destructing or the restructuring Sheng Cheng bioxin of molecule, and namely so-called gas phase (homogeneous phase) reaction generates; 3. solid ash surface generation heterogeneous catalytic reaction He Cheng bioxin, namely in flying dust, carbon residue, oxygen, hydrogen, chlorine etc. catalyze and synthesize intermediate product Huo bioxin at ash surface, or the predecessor in gas phase generates dioxin in ash surface catalysis.
According to the mechanism that bioxin is formed in Refuse Incineration Process, three classes before its prophylactico-therapeutic measures can be divided into burning, in burning, after burning.In order to reduce the generation probability of bioxin before combustion as far as possible, sending into garbage burning factory after the content of chlorinated organics in rubbish should being reduced as far as possible again and using.Therefore, before waste incineration, first carry out dechlorination process (separate from house refuse by the organochlorine in chlorinated organics, chlorine element is spun off from organic molecule and forms free chlorion), by removing organochlorine in rubbish as much as possible to control Cl in burning process
2with the generation of HCl, then suppress the generation of bioxin, thus reach minimizing organochlorine to the effect of the harm of environment.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of compound catalysis dechlorination agent.Use this compound catalysis dechlorination agent effectively can remove house refuse or organic chloride as the organochlorine in the chloride solid waste such as polyvinyl chloride (PVC), polyvinylidene chloride (PVDC).
Compound catalysis dechlorination agent of the present invention, is made up of the component of following weight percentage:
Combustion adjuvant 40% ~ 60%, activating agent 1% ~ 5%, chelating agent 15 ~ 20%, stabilizing agent 30% ~ 40%, the summation of said components is 100%; Wherein:
Described combustion adjuvant is one or more the combination in alcohol-group fuel;
Described activating agent by weight percentage, is made up of nanometer di-iron trioxide 20% ~ 40%, nano ferrous iron oxide 20% ~ 40% and nano ferriferrous oxide 20% ~ 40%;
Described chelating agent is one or more the combination in high fatty amine;
Described stabilizing agent by weight percentage, is made up of quartz 20% ~ 30%, apatite 20% ~ 30% and calper calcium peroxide 40% ~ 50%.
Compound catalysis dechlorination agent of the present invention is mainly used in the dechlorination process before consumer waste incineration, also can be applicable to the dechlorination process of waste or used plastics as PVC, PVDC.
The effect that each component of above-mentioned compound catalysis dechlorination agent is carried out in dechlorination process before consumer waste incineration is as follows:
When entering the process of dechlorination reaction device after the house refuse of drying mixes with antichlor, solid-state house refuse is under the effect of combustion adjuvant, catalysis focus is formed centered by activating agent, improve its surface temperature in dechlorination reaction device, thus dechlorination reaction can be carried out under relatively low reaction temperature, save the energy ezpenditure of dechlorination reaction, in addition, chelating agent in antichlor and activating agent interact, fatty amine as chelating agent easily forms amido free radical, and the reactivity of amido free radical is very high, its chlorine atom under the effect of activating agent easily and in organochlorine compound forms chloramines and adds and intermediate, thus reduce the reaction activity that organochlorine removes, and then carrying out further along with chemical reaction, hydrogen atom replaces chlorine atom and forms organic hydrocarbon or organic acid compound, and the chlorine atom in organochlorine compound finally formed inorganic chlorine ion be fixed on harmless treatment after house refuse in, and, under the effect of antichlor stabilizing agent of the present invention, the compositions such as the iron in the nitrogen in house refuse, sulphur and catalyst, calcium, silicon can be made to form rock-steady structure, thus make sulphur be fixed in house refuse, so that in the process of follow-up domestic garbage burning electricity generation, greatly can reduce the discharge capacity of sulfur dioxide, nitrogen oxide etc.
In technique scheme:
Described alcohol-group fuel is the straight or branched alcohols comprised containing 1 ~ 12 carbon, and these alcohols should be liquid, can be specifically methyl alcohol, ethanol, butanols, iso-heptanol or straight chain octanol etc., when combustion adjuvant is the combination of above-mentioned any two or more material, their proportioning can be any proportioning.
High fatty amine as chelating agent also claims fatty amine, refer to the large class organic amine compound of carbon chain lengths within the scope of C8 ~ C22, can be specifically aliphatic amine polyoxyethylene ether, decyl propyl ether amine, dodecyl propyl ether amine, lauryl amine or octadecylamine etc., also can be the combination of any two or more material in above-mentioned selection, now, their proportioning can be any proportioning.
Apatite in composition stabilizing agent can be specifically asparagolite, fluor-apatite, wlkeite, chlorapatite or saamite etc., and also can be the combination of any two or more material in above-mentioned selection, now, their proportioning can be any proportioning.
The preparation method of compound catalysis dechlorination agent of the present invention is: first the quartz in stabilizing agent and apatite are pulverized, then mix with other solid shape composition, mix afterwards again, to obtain final product with the component of liquid state.Under normal circumstances, be that the quartz in stabilizing agent and floats are broken to 40 ~ 200 orders.
The using method of compound catalysis dechlorination agent of the present invention is: by primary household garbage dewatering to moisture be 20 ~ 40%, house refuse is added to (or in PVC, PVDC in the ratio of 1 ~ 5% (percentage by weight), when the object processed is PVC and PVDC, PVC and PVDC need not carry out processed) in, mix rear feeding dechlorination reaction device, under 280 ~ 350 DEG C of conditions, process the effect that 10 ~ 30min can reach dechlorination.
Compared with prior art, compound catalysis dechlorination agent of the present invention adopts the four kinds of component assembly of combustion adjuvant, activating agent, chelating agent and stabilizing agent to form, four components synergy makes the organochlorine in house refuse remove rapidly, and changes into inorganic matter and be fixed in residue; Through the house refuse of dechlorination process in follow-up burning process, due to removing of organochlorine most in pre-treating technology, thus can effectively suppress Cl in journey
2with the generation of HCl, basic to eliminate because organochlorine causes dioxin emission, and due to the effect of wherein stabilizing agent, the discharge of sulfur dioxide, nitrogen oxide, flue dust etc. can be reduced simultaneously, make the exhaust emissions of waste incineration reach environmental emission standard.
Detailed description of the invention
With specific embodiment, the invention will be further described below, but the present invention is not limited to these embodiments.
The percentage related in following embodiment is all weight percentage.
Embodiment 1
One, compound catalysis dechlorination agent is composed as follows:
Combustion adjuvant: methyl alcohol (liquid state) 40kg;
Activating agent: 5kg, the nanometer di-iron trioxide by 30%, the nano ferrous iron oxide of 40% and the nano ferriferrous oxide of 30% form;
Chelating agent: aliphatic amine polyoxyethylene ether (liquid state) 20kg;
Stabilizing agent: 35kg, the quartz by 20%, the apatite (fluor-apatite) of 40% and the calper calcium peroxide of 40% form.
Two, preparation method:
First the quartz in stabilizing agent and apatite are crushed to 100 orders respectively, afterwards they are mixed with other solid state component, and then add liquid composition and mix, namely obtain compound catalysis dechlorination agent.
Embodiment 2
One, compound catalysis dechlorination agent is composed as follows:
Combustion adjuvant: ethanol (liquid state) 50kg;
Activating agent: 2kg, the nanometer di-iron trioxide by 20%, the nano ferrous iron oxide of 40% and the nano ferriferrous oxide of 40% form;
Chelating agent: decyl propyl ether amine (liquid state) 18kg;
Stabilizing agent: 30kg, the quartz by 30%, the apatite (asparagolite: fluor-apatite=1:1, weight ratio) of 25% and the calper calcium peroxide composition of 45%.
Two, preparation method:
First the quartz in stabilizing agent and apatite are crushed to 40 orders respectively, afterwards they are mixed with other solid state component, and then add liquid composition, mix, namely obtain compound catalysis dechlorination agent.
Embodiment 3
One, compound catalysis dechlorination agent is composed as follows:
Combustion adjuvant: butanols (liquid state) 40kg;
Activating agent: 5kg, the nanometer di-iron trioxide by 40%, the nano ferrous iron oxide of 35% and the nano ferriferrous oxide of 25% form;
Chelating agent: dodecyl propyl ether amine (liquid state) 15kg;
Stabilizing agent: 40kg, the quartz by 25%, the apatite (asparagolite: fluor-apatite: wlkeite: chlorapatite: saamite=5:1:1:1:2, weight ratio) of 25% and the calper calcium peroxide composition of 50%.
Two, preparation method:
First the quartz in stabilizing agent and apatite are crushed to 200 orders respectively, afterwards they are mixed with other solid state component, and then add liquid composition, mix, namely obtain compound catalysis dechlorination agent.
Embodiment 4
One, compound catalysis dechlorination agent is composed as follows:
Combustion adjuvant: straight chain octanol (liquid state) 54kg;
Activating agent: 1kg, the nanometer di-iron trioxide by 25%, the nano ferrous iron oxide of 35% and the nano ferriferrous oxide of 40% form;
Chelating agent: 15kg, is made up of the lauryl amine of 10% and the aliphatic amine polyoxyethylene ether of 90%;
Stabilizing agent: 30kg, the quartz by 30%, the apatite (chlorapatite: saamite=3:1, weight ratio) of 20% and the calper calcium peroxide composition of 50%.
Two, preparation method:
First the quartz in stabilizing agent and apatite are crushed to 80 orders respectively, afterwards they are mixed with other solid state component, and then add liquid composition, mix, namely obtain compound catalysis dechlorination agent.
Experimental example 1: the dechlorination experiment of waste vinylene chloride plastic
To simulate house refuse waste vinylene chloride plastic for handling object, the content of organic chloride of described waste polyvinyl chloride is 56.8%, is divided into 5 parts, for subsequent use.
The compound catalysis dechlorination agent that Example 1 ~ 4 is obtained respectively mixes with above-mentioned 4 parts of waste and old gathering respectively in identical ratio (accounting for 3% of waste polyethylene plastic weigh), and send into dechlorination reaction device (the prosperous chemical machinery Co., Ltd in Weihai hundred million of same model respectively, GSH-500L reactor) in, react the content of organochlorine in polyvinyl chloride after 10min, 20min, 30min under being determined at 300 DEG C of conditions respectively, result as described in Table 1.
Under similarity condition, remaining a waste vinylene chloride plastic is not added any antichlor to be sent in the dechlorination reaction device of same model, react the content of organochlorine in polyvinyl chloride after 10min, 20min, 30min under being determined at 300 DEG C of conditions respectively, result as described in Table 1.
Table 1:
Experimental example 2: the dechlorination experiment of house refuse
The house refuse being 40% by the urban original household garbage dewatering collected from Xiufeng District, Guilin to water content is handling object, and after testing, content of organic chloride is wherein 6.8%, is divided into 2 parts, for subsequent use.
Get the obtained compound catalysis dechlorination agent of above-described embodiment 1 in 2.5% ratio add above-mentioned a copy of it in the above-mentioned house refuse of dehydration, mix, send in dechlorination reaction device (Weihai hundred million prosperous chemical machinery Co., Ltd GSH-500L reactor), react the content of organochlorine in house refuse after 10min, 20min, 30min under being determined at 300 DEG C of conditions respectively, result as described in Table 2.
Under similarity condition, the above-mentioned house refuse of remaining portion through dewatering is not added any antichlor to be sent in the dechlorination reaction device of same model, react the content of organochlorine in house refuse after 10min, 20min, 30min under being determined at 300 DEG C of conditions respectively, result as described in Table 2.
Table 2:
From data in above-mentioned table 1 and table 2, after adding compound catalysis dechlorination agent of the present invention, effectively can improve the dechlorination rate of organochlorine in house refuse or organic chloride, at reaction conditions, after 10 ~ 20min process, dechlorination rate can reach more than 90%, thus can control the source of organochlorine from source, and then effectively control the generation of bioxin at later stage burning process.
Claims (2)
1. compound catalysis dechlorination agent, is characterized in that it is made up of the component of following weight percentage:
Combustion adjuvant 40% ~ 60%, activating agent 1% ~ 5%, chelating agent 15 ~ 20%, stabilizing agent 30% ~ 40%, the summation of said components is 100%; Wherein:
Described combustion adjuvant is one or more the combination in alcohol-group fuel; Described alcohol-group fuel is liquid, specifically methyl alcohol, ethanol, butanols, iso-heptanol or straight chain octanol;
Described activating agent by weight percentage, is made up of nanometer di-iron trioxide 20% ~ 40%, nano ferrous iron oxide 20% ~ 40% and nano ferriferrous oxide 20% ~ 40%;
Described chelating agent is one or more the combination in high fatty amine; Described high fatty amine is aliphatic amine polyoxyethylene ether, decyl propyl ether amine, dodecyl propyl ether amine, lauryl amine or octadecylamine;
Described stabilizing agent by weight percentage, is made up of quartz 20% ~ 30%, apatite 20% ~ 30% and calper calcium peroxide 40% ~ 50%.
2. compound catalysis dechlorination agent according to claim 1, is characterized in that: described apatite is one or more the combination be selected from asparagolite, fluor-apatite, wlkeite, chlorapatite and saamite.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210330235.8A CN102824718B (en) | 2012-09-07 | 2012-09-07 | Compound catalytic dechlorinating agent |
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|---|---|---|---|
| CN201210330235.8A CN102824718B (en) | 2012-09-07 | 2012-09-07 | Compound catalytic dechlorinating agent |
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| CN102824718A CN102824718A (en) | 2012-12-19 |
| CN102824718B true CN102824718B (en) | 2015-04-15 |
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| CN109092850A (en) * | 2018-07-26 | 2018-12-28 | 安徽安江环保科技有限公司 | A method of solidifying garbage flying ash using chelating agent |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4140746A (en) * | 1976-11-17 | 1979-02-20 | Mineral Process Licensing Corporation B.V. | Recovery of chlorine values from iron chloride by-produced in chlorination of ilmenite and the like |
| NL7804568A (en) * | 1978-04-27 | 1979-10-30 | Mineral Process Licensing Corp | Recovery of chlorine from iron chloride(s) - obtd. in the chlorination of iron-contg. titanium ores, by partial dechlorination in the presence of a reducing agent, followed by oxidn. |
| JPH05182174A (en) * | 1991-12-26 | 1993-07-23 | Nisshin Kagaku Kogyo Kk | Magnetic recording medium |
| CN1768905A (en) * | 2004-11-01 | 2006-05-10 | 中国科学院生态环境研究中心 | Dechlorination agent and preparation method thereof |
| CN101147864A (en) * | 2007-10-12 | 2008-03-26 | 南开大学 | Method for preparing novel catalytic reduction dechlorinating agent |
-
2012
- 2012-09-07 CN CN201210330235.8A patent/CN102824718B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4140746A (en) * | 1976-11-17 | 1979-02-20 | Mineral Process Licensing Corporation B.V. | Recovery of chlorine values from iron chloride by-produced in chlorination of ilmenite and the like |
| NL7804568A (en) * | 1978-04-27 | 1979-10-30 | Mineral Process Licensing Corp | Recovery of chlorine from iron chloride(s) - obtd. in the chlorination of iron-contg. titanium ores, by partial dechlorination in the presence of a reducing agent, followed by oxidn. |
| JPH05182174A (en) * | 1991-12-26 | 1993-07-23 | Nisshin Kagaku Kogyo Kk | Magnetic recording medium |
| CN1768905A (en) * | 2004-11-01 | 2006-05-10 | 中国科学院生态环境研究中心 | Dechlorination agent and preparation method thereof |
| CN101147864A (en) * | 2007-10-12 | 2008-03-26 | 南开大学 | Method for preparing novel catalytic reduction dechlorinating agent |
Non-Patent Citations (2)
| Title |
|---|
| 《synergic effect of calcium oxide and ironIII oxide on the dechlorination of hexachlorobenzene》;maxiaodong;《chemosphere》;20050831;第60卷(第6期);796-801 * |
| 水热降解聚氯乙烯废弃物的研究;张猛等;《实验室科学》;20090628(第03期);58-59 * |
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