CN100377989C - Method for preparing hydrogen utilizing waste plastics - Google Patents
Method for preparing hydrogen utilizing waste plastics Download PDFInfo
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- CN100377989C CN100377989C CNB2006100167359A CN200610016735A CN100377989C CN 100377989 C CN100377989 C CN 100377989C CN B2006100167359 A CNB2006100167359 A CN B2006100167359A CN 200610016735 A CN200610016735 A CN 200610016735A CN 100377989 C CN100377989 C CN 100377989C
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Abstract
The present invention belongs to the field for preparing hydrogen by waste plastics. The present invention discloses a method for obtaining the hydrogen by catalytic cracking at the temperature of 500 DEG C to 950 DEG C in inert atmosphere under the compound catalytic action of halogen containing compound and ferrum, cobalt and nickel catalyst by using waste plastics as raw materials. The raw materials which are used for the method are the waste plastics which contain rich hydrogen, price is low, and the high added value chemical recovery of the waste plastics is realized. The operation of the method is simple, polyvinyl chloride does not need to be separated from the raw materials, and even the polyvinyl chloride is used as a catalysis component; thus, the difficulty for sorting and treating polymer is simplified. The yield of the hydrogen which is obtained in the method is high, and the hydrogen is easy to separate.
Description
Technical field
The invention belongs to and utilize waste or used plastics to prepare the hydrogen field, disclose a kind of method of utilizing waste or used plastics to prepare hydrogen.
Technical background:
In recent years, along with the fast development of plastics industry, corresponding plastic refuse is also accumulated year by year.Because plastics itself can not be degraded under field conditions (factors), thereby the waste or used plastics of accumulating has year by year formed the serious environmental pollution, promptly said " white pollution ".Simultaneously, waste or used plastics is still containing huge renewable resource, and the existence of " white pollution " is the huge waste of limited earth resources.Therefore, reclaiming and utilizing waste plastics is the key point of plastics industry sustainable development in this century, is again the important behave that solves ecological environmental pollution.
Polyethylene accounts for 48% in the plastic waste, and polypropylene accounts for 18%, and polystyrene accounts for 16%, and polyvinyl chloride accounts for 7%.The reclaiming and utilizing waste plastics technological method mainly can reduce three classes, and energy law and chemical cracking absorption method are reclaimed in the absorption method of promptly regenerating, burning.The product properties that the regeneration absorption method obtains is relatively poor, and added value of product is not high, and the termination of these salvage materials still is chemical recovery or burning in addition; Burning and reclaiming the energy also is the common method of treatment of waste plastics, but the plastic waste burning not only can produce a large amount of greenhouse gases---carbonic acid gas, and can produce hazardous compounds such as Polycyclic aromatic hydrocarbons compound, acidic substance, carbon monoxide, heavy metal compound, these materials pollute the environment as directly entering atmosphere, and HUMAN HEALTH is worked the mischief; The chemical cracking absorption method is to place the sealed vessel heating of anaerobic or hypoxemia to make it be cracked into the method for low molecular compound the plastic waste with removal of contamination, but this method is to accounting for the polyethylene of waste or used plastics 48% at present, 18% polypropylene, to consider not only in the recovery of 7% polyvinyl chloride that polyvinyl chloride emits the negative impact of hydrogenchloride, and the product that obtains of this method is used for fuel with gasoline and diesel oil more, and termination also has carbonic acid gas to emit.
Hydrogen is a kind of ideal secondary energy, possesses energy density height, free of contamination characteristics, and along with the various Hydrogen Energies that with the fuel cell are representative are utilized the fast development of technology, following demand will significantly rise.Present business-like Sweet natural gas, methyl alcohol, fossil oil vapor reforming hydrogen productions such as gasoline will produce the greenhouse gases carbonic acid gas inevitably.Plasma method is the effective means that hydro carbons is converted into carbon and hydrogen that occurs at present, but the use temperature height, and power consumption is big, the technology more complicated.University of California's (China Patent No.: 00816840.7) adopt two-stage process, make carbonaceous material and hydrogen reaction obtain fuel gas earlier, obtain hydrogen and lime carbonate with water and calcium oxide reaction again, calcination of calcium carbonate reclaims calcium oxide, thereby realization hydrogen separates with carbonic acid gas, but this device and technology are all comparatively complicated, and do not reduce the generation of carbonic acid gas.Waste or used plastics is mainly by hydrocarbon elementary composition, wherein the protium amount is very high, China applies for a patent (application number 200510017038.0), and to disclose a kind of olefin polymer be raw material, under the modified montmorillonoid of nickel catalyzator and proton type and ammonium exchange, the effect of molecular sieve promotor, cracking prepares hydrogen in inert atmosphere.But modified montmorillonoid, the molecular sieve of proton type that this method is used and ammonium exchange, price is higher, and this patent application only is confined to polyolefine in addition.
Summary of the invention:
The present invention is a kind of method of utilizing waste or used plastics to prepare hydrogen.Be a kind of be raw material with the waste or used plastics, under halide-containing and the effect of char forming catalyst assembly catalyze, in inert atmosphere, obtain the method for hydrogen in 500 ℃ of-950 ℃ of following catalytic pyrolysiss.
Its concrete steps and condition are as follows:
To contain at least a halide-containing for polyvinyl chloride, polyvinylidene dichloride, clorafin, brominated paraffin, decabromodiphenyl oxide, fluorinated ethylene propylene, aluminum chloride, iron(ic) chloride, cupric chloride, cuprous chloride, nickelous chloride, cobalt chloride, zinc chloride, polymerize aluminum chloride, aluminium iron polychloride, ammonium chloride, brometo de amonio or ammonium iodide, the char forming catalyst of at least a iron content, cobalt or nickel metallic element and at least a waste polyethylene, waste polypropylene or deposed polystyrene melt blending prepare the plastic waste blend.
Under inert atmosphere, the plastic waste blend that the obtains gas that decomposition obtains under 500 ℃-950 ℃ through cooling, alkali cleaning, is promptly obtained hydrogen.
The proportioning of above-mentioned plastic waste blend is: the weight ratio that halogen accounts for the plastic waste blend is 0.01-20%, and the weight ratio that iron, cobalt or the nickel metallic element that plays into the charcoal effect in the catalyzer accounts for the plastic waste blend is 0.05-40%.
Above-mentioned char forming catalyst is the catalyzer of active site with iron, cobalt or nickel mainly, and it is:
(1) iron, cobalt or the nickel with 0 valency is the catalyzer of main active site, comprises nano level iron, cobalt or nickel and loads on iron, cobalt or nickel catalyzator on silicon oxide, aluminum oxide, silica-alumina, molecular sieve, diatomite, polynite or the carbon nanotube;
(2) oxide compound of iron, cobalt or nickel comprises the oxide compound of the iron, cobalt or the nickel that load on silicon oxide, aluminum oxide, silica-alumina, molecular sieve, diatomite, polynite or the carbon nanotube;
(3) oxyhydroxide of iron, cobalt or nickel, subcarbonate, oxalate or formate comprise these compound loaded loaded catalysts that forms on silicon oxide, aluminum oxide, silica-alumina, molecular sieve, diatomite, polynite or carbon nanotube; Or iron, cobalt or nickel are a kind of or any two or three houghite that forms with aluminium element.
Advantage of the present invention:
The present invention adopts the assembly catalyze effect of halogen and char forming catalyst that plastic waste is cracked into hydrogen and carbon material efficiently, has realized the efficient at low cost chemical recovery of plastic waste.More important is to adopt the part of waste polyvinyl chloride as catalyzer among the present invention, need not it is separated just directly cracking, and the chlorine element is mainly emitted with the form of hydrogenchloride, is easy to separate.
Embodiment:
Gas volume in the following example is the volume under the normal temperature and pressure.
Embodiment 1
The ammonium iodide, waste polypropylene/polyethylene composite, black nickel oxide that with iodine content are 84% weight ratio be by weight 24: 66: 10 melt blendings, preparation plastic waste blend; Wherein to account for plastic waste blend weight ratio be 20% to iodine, and it is 6% that nickel accounts for plastic waste blend weight ratio.
Get above-mentioned blend 10 and restrain 500 ℃ of heating in the inert atmosphere that is put in silica tube, decomposition gas gets 8.3 liters of hydrogen through cooling, alkali cleaning.
Embodiment 2
The clorafin, waste polypropylene, deposed polystyrene, nanometer iron powder that with cl content are 70% weight ratio were by weight 1: 30: 29: 40 melt blendings, preparation plastic waste blend; Wherein to account for plastic waste blend weight ratio be 0.7% to chlorine, and it is 40% that iron accounts for plastic waste blend weight ratio.
Get above-mentioned blend 10 and restrain 950 ℃ of heating in the inert atmosphere that is put in silica tube, decomposition gas gets 5.6 liters of hydrogen through cooling, alkali cleaning.
Embodiment 3
With fluorinated ethylene propylene, the waste polypropylene of fluorine-containing 40% weight ratio, contain cobalt 10% the montmorillonite load cobalt oxide by weight 0.025: 79.975: 20 melt blending, preparation plastic waste blend; Wherein to account for plastic waste blend weight ratio be 0.01% to fluorine, and it is 2% that cobalt accounts for plastic waste blend weight ratio.
Get above-mentioned blend 10 and restrain 550 ℃ of heating in the inert atmosphere that is put in silica tube, decomposition gas gets 7.8 liters of hydrogen through cooling, alkali cleaning.
Embodiment 4
With cl content be aluminum chloride, waste polyethylene, nickeliferous 0.5% the molecular sieve carried nickel formate of 40% weight ratio by weight 1: 98: 1 melt blending, preparation plastic waste blend; Wherein to account for plastic waste blend weight ratio be 0.4% to chlorine, and it is 0.05% that nickel accounts for plastic waste blend weight ratio.
Get above-mentioned blend 10 and restrain 650 ℃ of heating in the inert atmosphere that is put in silica tube, decomposition gas gets 8.6 liters of hydrogen through cooling, alkali cleaning.
Embodiment 5
The tripolite loading ironic oxalate of nickelous chloride, deposed polystyrene, iron content 10% that with cl content is 30% weight ratio is by weight 1: 98: 1 melt blending, preparation plastic waste blend; Wherein to account for plastic waste blend weight ratio be 0.3% to chlorine, and it is 1% that iron accounts for plastic waste blend weight ratio.
Get above-mentioned blend 10 and restrain 750 ℃ of heating in the inert atmosphere that is put in silica tube, decomposition gas gets 3.0 liters of hydrogen through cooling, alkali cleaning.
Embodiment 6
The cupric chloride of chloride 40% weight ratio, chloride 35% cuprous chloride, waste polyethylene, nickeliferous and cobalt are 10% aluminium oxide-silicon oxide load 0 valency nickel cobalt by 25: 10: 60: 5 weight ratio melting mixing, preparation plastic waste blend; Wherein to account for plastic waste blend weight ratio be 14% to chlorine, and it is 0.5% that iron accounts for plastic waste blend weight ratio.
Get above-mentioned blend 10 and restrain 800 ℃ of heating in the inert atmosphere that is put in silica tube, decomposition gas gets 5.0 liters of hydrogen through cooling, alkali cleaning.
Embodiment 7
With the decabromodiphenyl oxide of brominated 83% weight ratio, chloride 40% iron(ic) chloride, waste polypropylene, nickel hydroxide, basic nickel carbonate by 10: 5: 83: the weight ratio melting mixing prepared the plastic waste blend in 1: 1; Wherein to account for plastic waste blend weight ratio altogether be 11% for bromine and chlorine, and it is 1.2% that nickel accounts for plastic waste blend weight ratio.
Get above-mentioned blend 10 and restrain 900 ℃ of heating in the inert atmosphere that is put in silica tube, decomposition gas gets 10.0 liters of hydrogen through cooling, alkali cleaning.
Embodiment 8
Useless polyvinylidene dichloride, waste polyethylene, the cobaltous acetate of the brometo de amonio of brominated 80% weight ratio, chloride 65% weight ratio were pressed 1: 1: 68: 30 weight ratio melting mixing, preparation plastic waste blend; Wherein to account for plastic waste blend weight ratio altogether be 1.45% for bromine and chlorine, and it is 6% that cobalt accounts for plastic waste blend weight ratio.
Get above-mentioned blend 10 and restrain 730 ℃ of heating in the inert atmosphere that is put in silica tube, decomposition gas gets 8.0 liters of hydrogen through cooling, alkali cleaning.
Embodiment 9
With the carbon nanotube loaded nickel of the cobalt chloride of the polymerize aluminum chloride of chloride 20% weight ratio, chloride 25% weight ratio, waste polypropylene, nickeliferous 1% weight ratio by 1: 1: 93: 5 weight ratio melting mixing, preparation plastic waste blend; Wherein to account for plastic waste blend weight ratio be 0.4% to chlorine, and it is 0.05% that nickel accounts for plastic waste blend weight ratio.
Get above-mentioned blend 10 and restrain 680 ℃ of heating in the inert atmosphere that is put in silica tube, decomposition gas gets 7.0 liters of hydrogen through cooling, alkali cleaning.
Embodiment 10
Zinc chloride, waste polypropylene/polyethylene composite, the cobaltous hydroxide of the brominated paraffin of brominated 40% weight ratio, chloride 50% weight ratio were pressed 1: 1: 93: 5 weight ratio melting mixing, preparation plastic waste blend; Wherein to account for plastic waste blend weight ratio be 0.9% for chlorine and bromine, and it is 3% that cobalt accounts for plastic waste blend weight ratio.
Get above-mentioned blend 10 and restrain 650 ℃ of heating in the inert atmosphere that is put in silica tube, decomposition gas gets 9.0 liters of hydrogen through cooling, alkali cleaning.
Embodiment 11
With aluminium iron polychloride, the waste polypropylene of the ammonium chloride of chloride 65% weight ratio, chloride 20% weight ratio, contain cobalt 20% weight ratio and nickeliferous 25% weight ratio nickel cobalt aluminium houghite by 1: 1: 93: 5 weight ratio melting mixing, preparation plastic waste blend; Wherein to account for plastic waste blend weight ratio be 0.85% to chlorine, and it is 2.25% that cobalt and nickel account for plastic waste blend weight ratio.
Get above-mentioned blend 10 and restrain 750 ℃ of heating in the inert atmosphere that is put in silica tube, decomposition gas gets 10.0 liters of hydrogen through cooling, alkali cleaning.
Claims (2)
1. method of utilizing waste or used plastics to prepare hydrogen, it is characterized in that: with at least a halide-containing for polyvinyl chloride, polyvinylidene dichloride, clorafin, brominated paraffin, decabromodiphenyl oxide, fluorinated ethylene propylene, aluminum chloride, iron(ic) chloride, cupric chloride, cuprous chloride, nickelous chloride, cobalt chloride, zinc chloride, polymerize aluminum chloride, aluminium iron polychloride, ammonium chloride, brometo de amonio or ammonium iodide, the char forming catalyst of at least a iron content, cobalt or nickel metallic element and at least a waste polyethylene, waste polypropylene or deposed polystyrene melt blending prepare the plastic waste blend; Described char forming catalyst is to be the catalyzer of active site with iron, cobalt or nickel mainly;
The proportioning of described plastic waste blend is: the weight ratio that the halogen of halide-containing accounts for the plastic waste blend is 0.01-20%, and the weight ratio that iron, cobalt or the nickel metallic element that plays into the charcoal effect in the catalyzer accounts for the plastic waste blend is 0.05-40%;
Under inert atmosphere, the plastic waste blend that the obtains gas that decomposition obtains under 500 ℃-950 ℃ through cooling, alkali cleaning, is promptly obtained hydrogen.
2. a kind of method of utilizing waste or used plastics to prepare hydrogen as claimed in claim 1 or 2 is characterized in that: described char forming catalyst is the catalyzer of active site with iron, cobalt or nickel mainly, and it is:
(1) iron, cobalt or the nickel with 0 valency is the catalyzer of main active site, comprises nano level iron, cobalt or nickel and loads on iron, cobalt or nickel catalyzator on silicon oxide, aluminum oxide, silica-alumina, molecular sieve, diatomite, polynite or the carbon nanotube;
(2) oxide compound of iron, cobalt or nickel comprises the oxide compound of the iron, cobalt or the nickel that load on silicon oxide, aluminum oxide, silica-alumina, molecular sieve, diatomite, polynite or the carbon nanotube;
(3) oxyhydroxide of iron, cobalt or nickel, subcarbonate, oxalate or formate comprise these compound loaded loaded catalysts that forms on silicon oxide, aluminum oxide, silica-alumina, molecular sieve, diatomite, polynite or carbon nanotube; Or iron, cobalt or nickel are a kind of or any two or three houghite that forms with aluminium element.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100167359A CN100377989C (en) | 2006-03-31 | 2006-03-31 | Method for preparing hydrogen utilizing waste plastics |
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| CNB2006100167359A CN100377989C (en) | 2006-03-31 | 2006-03-31 | Method for preparing hydrogen utilizing waste plastics |
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| CN1850583A CN1850583A (en) | 2006-10-25 |
| CN100377989C true CN100377989C (en) | 2008-04-02 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102491308A (en) * | 2011-11-25 | 2012-06-13 | 卓心康 | Method for synthesis of carbon nanostructure material by using organic material |
| CN107934938A (en) * | 2017-12-06 | 2018-04-20 | 武汉光谷环保科技股份有限公司 | The method that two-phase method catalytic pyrolysis waste plastic prepares carbon nanotubes |
| CN111689466A (en) * | 2020-05-27 | 2020-09-22 | 深圳市中科纳米科技有限公司 | Comprehensive treatment method and treatment system for organic waste |
| CN114538415B (en) * | 2022-02-25 | 2024-03-26 | 暨南大学 | Method for preparing carbon nano tube by taking wax as carbon source |
| CN115650209A (en) * | 2022-11-17 | 2023-01-31 | 深圳轻碳新能源科技有限公司 | Method for preparing nano carbon material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1136325A (en) * | 1993-10-04 | 1996-11-20 | 德士古发展公司 | Hydrothermal treatment and partial oxidation of plastic materials |
| JP2000319671A (en) * | 1999-03-11 | 2000-11-21 | Ebara Corp | Operation control method of two-stage waste gasification system waste |
| EP1195353A1 (en) * | 1999-04-02 | 2002-04-10 | Ebara Corporation | Method and apparatus for production of hydrogen by gasification of combusible material |
| WO2005037510A2 (en) * | 2003-10-21 | 2005-04-28 | Nippon Steel Corporation | Method of recycling waste plastic and method of molding |
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- 2006-03-31 CN CNB2006100167359A patent/CN100377989C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1136325A (en) * | 1993-10-04 | 1996-11-20 | 德士古发展公司 | Hydrothermal treatment and partial oxidation of plastic materials |
| JP2000319671A (en) * | 1999-03-11 | 2000-11-21 | Ebara Corp | Operation control method of two-stage waste gasification system waste |
| EP1195353A1 (en) * | 1999-04-02 | 2002-04-10 | Ebara Corporation | Method and apparatus for production of hydrogen by gasification of combusible material |
| WO2005037510A2 (en) * | 2003-10-21 | 2005-04-28 | Nippon Steel Corporation | Method of recycling waste plastic and method of molding |
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Owner name: CHANGZHOU INSTITUTE OF ENERGY STORAGE MATERIALS + Free format text: FORMER OWNER: CHANGCHUN INST. OF APPLIED CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20131010 |
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Effective date of registration: 20131010 Address after: Changzhou City, Jiangsu province Hehai road 213000 No. 9 Patentee after: Changzhou Institute of Energy Storage Materials & Devices Address before: 130022 Changchun people's street, Jilin, No. 5625 Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences |
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