CN102380401B - Solid super acidic catalyst for waste plastic catalytic pyrolysis as well as manufacture method and application thereof - Google Patents
Solid super acidic catalyst for waste plastic catalytic pyrolysis as well as manufacture method and application thereof Download PDFInfo
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- CN102380401B CN102380401B CN 201110223368 CN201110223368A CN102380401B CN 102380401 B CN102380401 B CN 102380401B CN 201110223368 CN201110223368 CN 201110223368 CN 201110223368 A CN201110223368 A CN 201110223368A CN 102380401 B CN102380401 B CN 102380401B
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- 239000002699 waste material Substances 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 239000007787 solid Substances 0.000 title claims abstract description 37
- 239000004033 plastic Substances 0.000 title claims abstract description 25
- 229920003023 plastic Polymers 0.000 title claims abstract description 25
- 238000007233 catalytic pyrolysis Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title abstract description 13
- 230000002378 acidificating effect Effects 0.000 title abstract 6
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 18
- 239000000295 fuel oil Substances 0.000 claims abstract description 12
- -1 transition metal modified tin Chemical class 0.000 claims abstract description 11
- 238000011084 recovery Methods 0.000 claims abstract description 9
- 238000004821 distillation Methods 0.000 claims description 25
- 239000003930 superacid Substances 0.000 claims description 25
- 239000010802 sludge Substances 0.000 claims description 24
- 238000005336 cracking Methods 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 150000003624 transition metals Chemical class 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 9
- 239000002283 diesel fuel Substances 0.000 claims description 8
- 239000003502 gasoline Substances 0.000 claims description 8
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 8
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 7
- 239000005695 Ammonium acetate Substances 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 229940043376 ammonium acetate Drugs 0.000 claims description 7
- 235000019257 ammonium acetate Nutrition 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 150000003608 titanium Chemical class 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 3
- 241000370738 Chlorion Species 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims 3
- 239000010893 paper waste Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 229910006698 SnO2-Fe2O3 Inorganic materials 0.000 abstract 2
- 239000002893 slag Substances 0.000 abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000002075 main ingredient Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 101710134784 Agnoprotein Proteins 0.000 description 5
- 241000984082 Amoreuxia Species 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical class ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000011973 solid acid Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- JUHDUIDUEUEQND-UHFFFAOYSA-N methylium Chemical group [CH3+] JUHDUIDUEUEQND-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 description 1
- LOTKRQAVGJMPNV-UHFFFAOYSA-N 1-fluoro-2,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C([N+]([O-])=O)=C1 LOTKRQAVGJMPNV-UHFFFAOYSA-N 0.000 description 1
- QZYHIOPPLUPUJF-UHFFFAOYSA-N 3-nitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1 QZYHIOPPLUPUJF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Catalysts (AREA)
Abstract
The invention dislcoses a solid super acidic catalyst for waste plastic catalytic pyrolysis as well as a manufacture method and an application thereof, which aims at solving the problems that papermaking waste slag generated by the waste paper recovery reutilization can not be effectively utilized, and the huge pressure is caused on the environment. The solid super acidic catalyst is transition metal modified tin system solid super acidic, and the expression formula of the transition metal modified tin system solid super acidic is one of the following expression formulas: SO4<2->/SnO2-Fe2O3, S2O8<2->/SnO2-Fe2O3, SO4<2->/SnO2-ZnO, S2O8<2->/SnO2-ZnO, O4<2->/SnO2-TiO2 and S2O8<2->/SnO2-TiO2. The solid super acidic catalyst has the advantages that the production cost is low, the manufacture is easy, and waste plastics of main ingredients of the papermaking waste slag can be effectively prepared into fuel oil through the catalytic pyrolysis.
Description
Technical field
The present invention relates to a kind of catalyst, particularly a kind of waste plastics catalytic pyrolysis usefulness solid super acid catalyst and manufacture method thereof, application.
Background technology
The waste paper recycling is an effective way that solves papermaking shortage of raw materials problem, can saving resource, reduce cost, and be the important measures that China's paper industry solves the fibrous raw material difficulty.But, to produce a large amount of waste residues after utilizing regenerated papermaking.Several hundred paper mills, Fuyang, Zhejiang city production and sales volume accounts for more than 60% of domestic market ratio, produces about more than 2000 tons of waste residues every day at present by statistics, and the main component of waste residue is waste plastics by analysis, and annual generation waste plastics is 151200 tons.Because plastic refuse is not perishable, had a strong impact on the ecological environment of the earth.Therefore, the improvement of waste plastics is very urgent.
Solid super-strong acid is a kind of solid acid catalyst of Recent study and exploitation, is to compare 100%H
2SO
4Acid strength strong solid acid also, its acid strength is with special (Hammett) Acidity function H of Harmer
0Expression, known 100%H
2SO
4Special (Hammett) Acidity function H of Harmer
0=-11.93, so every H
0＜-11.93 solid all is called solid super-strong acid.From SO in 1979
4 2-/ M
xO
ySince the preparation method of type solid super-strong acid is in the news first, SO
4 2-/ M
xO
yThe type solid super-strong acid is as a kind of novel heterogeneous catalysis, generally has not etching apparatus, pollution is little, high temperature resistant, post processing is simple, the advantage such as easily separated, reusable, has obtained broad research in the acid catalysis field.The efficient solid acid catalyst of Development of Novel is for waste sludge from paper mill---the made from used plastics oil tech has great significance.
Liu Ming, Zheng Dianmo, Hu Ping, " research of Catalytic Cracking of Waste Plastics for Producing Fuel Oil ", the Jiangxi chemical industry, 2006.01. once report mixed with flyash, aluminium chloride, alumina silicate, ammonium molybdate and formed catalyst for cracking, but the cost of material of this catalyst and manufacturing expense are quite high, have limited promoting the use of of this catalyst.
Summary of the invention
The object of the invention is to solve the waste sludge from paper mill that the waste paper recycling produces and can not get effective utilization, bring the problem of immense pressure to environment, provide a kind of production cost low, easy to manufacture, can be effectively with the solid super acid catalyst of waste sludge from paper mill principal component pyrolysis of waste plastic for preparing for one-tenth fuel oil, it can be turned waste into wealth, and alleviates environmental pressure.
The present invention also provides the preparation method of this solid super acid catalyst, and the preparation method is simple, and cost is low, is fit to large-scale production.
Solid super acid catalyst of the present invention is particularly suitable for processing the waste sludge from paper mill that the waste paper recycling produces.
The technical solution adopted for the present invention to solve the technical problems is: a kind of waste plastics catalytic pyrolysis solid super acid catalyst, described solid super acid catalyst is that transition metal modified tin is solid super-strong acid, and the expression formula that described transition metal modified tin is solid super-strong acid is a kind of in the following formula: SO
4 2-/ SnO
2-Fe
2O
3, S
2O
8 2-/ SnO
2-Fe
2O
3, SO
4 2-/ SnO
2-ZnO, S
2O
8 2-/ SnO
2-ZnO, O
4 2-/ SnO
2-TiO
2, S
2O
8 2-/ SnO
2-TiO
2
Catalyst of the present invention belongs to the solid acid catalyst, and reaction mechanism can be explained with the carbonium ion theory.The alkene that thermal cracking produces long carbochain occurs first in waste sludge from paper mill (waste plastics), and then alkene enters and obtains H on the catalyst surface
+And the formation carbonium ion, carbonium ion fragments into first primary in the β position, secondary carbon ion, then is isomerizated into more stable tertiary carbon cation, and last, stable tertiary carbon cation is with H
+Return catalyst, itself becomes alkene.Isomerization can make non-straight-chain hydrocarbons molecule greatly increase, and the straight-chain hydrocarbons molecule reduces.The preferred SO of catalyst of the present invention
4 2-/ SnO
2-Fe
2O
3Or S
2O
8 2-/ SnO
2-Fe
2O
3
As preferably, described transition metal modified tin is that the mol ratio of tin and transition metal is 2 ~ 20:1 in the solid super-strong acid.
A kind of waste plastics catalytic pyrolysis is as follows with the described preparation method's step of preparation method of solid super acid catalyst:
1. with the soluble-salt of solubility pink salt and transition metal according to mole proportioning tin: the ratio of transition metal=2 ~ 20:1 is dissolved in the distilled water, mixes to get mixed liquor; The soluble-salt that the amount of distilled water satisfies solubility pink salt and transition metal dissolves get final product fully, even the quantity of solvent of solute dissolving;
2. add alkali lye in the mixed liquor that 1. obtains to step and regulate pH to 8 ~ 9, ageing 12 ~ 48h under the room temperature, suction filtration gets filter cake;
3. filter cake is after removal of impurities, oven dry, grinding, with the H of 0.2 ~ 5mol/L
2SO
4Solution or (NH
4)
2S
2O
8Solution carries out impregnation process, after filtration, the drying, gets finished product after the roasting in air atmosphere.The time of impregnation process is 5 minutes ~ 3 hours.
As preferably, the soluble-salt of transition metal is selected from a kind of in soluble ferric iron salt, soluble zinc salt, the solubility titanium salt.
As preferably, described solubility pink salt is SnCl
45H
2O, described soluble ferric iron salt is FeCl
36H
2O, described soluble zinc salt are ZnCl
2, described solubility titanium salt is TiCl
4
As preferably, the alkali lye of step described in 2. is concentrated ammonia liquor.
As preferably, the H of step described in 3.
2SO
4The concentration of solution is 2 ~ 3mol/L, described (NH
4)
2S
2O
8Concentration be 1 ~ 2mol/L.
As preferably, the sintering temperature of step described in 3. is 500 ~ 600 ℃, and roasting time is 3 ~ 8h.
As preferably, the removal of impurities of step described in 3. be for removing chlorion with filter cake with the ammonium acetate solution washing of mass concentration 2%, and described bake out temperature is that 100 ℃, time are 24h, after grinding 100 mesh sieves.
A kind of waste plastics catalytic pyrolysis is applied to the processing of waste sludge from paper mill with solid super acid catalyst.
The invention has the beneficial effects as follows:
1, production cost is low, easy to manufacture, can be effectively becomes fuel oil with waste sludge from paper mill principal component pyrolysis of waste plastic for preparing is standby, thereby alleviates environmental pressure, increases economic efficiency;
2, be particularly suitable for the suitability for industrialized production of certain scale.
The specific embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1: the preparation of catalyst-1
Get commercially available SnCl
45H
2O 20g and FeCl
36H
2O 1.71g(Chemical Reagent Co., Ltd., Sinopharm Group produces) be dissolved in the 200 mL distilled water, stir lower 25 %(w/w of adding) to transfer pH be 8 to ammoniacal liquor, and ageing 24h under the room temperature, suction filtration is removed Cl through the washing of 2% ammonium acetate solution
-(with the AgNO of 0.1 mol/L
3Check), filter cake ground 100 orders at 100 ℃ of lower dry 24h, placed 1mol/L (NH
4)
2S
2O
8Flood in the solution (15 mL/g), then filter, oven dry, 550 ℃ of roasting 5h obtain described S
2O
8 2-/ SnO
2-Fe
2O
3Catalyst (Fe/ Sn mole proportioning is 1:9).
Embodiment 2: the preparation of catalyst-2
Get commercial SnCl
45H
2O 20g and FeCl
36H
2O 3.86g(Chemical Reagent Co., Ltd., Sinopharm Group produces) be dissolved in the 200 mL distilled water, stir lower 25 %(w/w of adding) to transfer pH be 9 to ammoniacal liquor, and ageing 48h under the room temperature, suction filtration is removed Cl through the washing of 2% ammonium acetate solution
-(with the AgNO of 0.1 mol/L
3Check), filter cake ground 100 orders at 100 ℃ of lower dry 24h, placed 2 mol/L H
2SO
4Carry out impregnation process in the solution (15 mL/g), then filter, oven dry, 600 ℃ of roasting 3h obtain described SO
4 2-/ SnO
2-Fe
2O
3Catalyst (Fe/ Sn mole proportioning is 1:4).
Embodiment 3: the preparation of catalyst-3
Get commercial SnCl
45H
2O 20g and FeCl
36H
2O 2.51g(Chemical Reagent Co., Ltd., Sinopharm Group produces) be dissolved in 200 mL distillation and stir lower 25 %(w/w of adding) to transfer pH be 8 to ammoniacal liquor, ageing 12h under the room temperature, suction filtration is removed Cl through the washing of 2% ammonium acetate solution
-(with the AgNO of 0.1 mol/L
3Check), filter cake ground 100 orders at 100 ℃ of lower dry 24h, placed (the NH of 2mol/L
4)
2S
2O
8Impregnation process in the solution (15 mL/g) is then filtered, oven dry, and 550 ℃ of roasting 8h obtain described S
2O
8 2-/ SnO
2-Fe
2O
3Catalyst (Fe/ Sn mole proportioning is 1:6).
Embodiment 4: the preparation of catalyst-4
Get commercial SnCl
45H
2O 20g and ZnCl
20.87g(Chemical Reagent Co., Ltd., Sinopharm Group produces) be dissolved in 200 mL distilled water, stir lower 25 %(w/w of adding) to transfer pH be 8 to ammoniacal liquor, and ageing 24h under the room temperature, suction filtration is removed Cl through the washing of 2% ammonium acetate solution
-(with the AgNO of 0.1 mol/L
3Check), filter cake ground 100 orders at 100 ℃ of lower dry 24h, placed the H of 3mol/L
2SO
4Impregnation process in the solution (15 mL/g) is then filtered, oven dry, and 550 ℃ of roasting 8h obtain described SO
4 2-/ SnO
2-ZnO catalyst (Zn/Sn mole proportioning is 1:9).
Embodiment 5: the preparation of catalyst-5
Get commercial SnCl
45H
2O 20g and TiCl
43.65g(Chemical Reagent Co., Ltd., Sinopharm Group produces) be dissolved in 200 mL distilled water, stir lower 25 %(w/w of adding) to transfer pH be 8 to ammoniacal liquor, and ageing 24h under the room temperature, suction filtration is removed Cl through the washing of 2% ammonium acetate solution
-(with the AgNO of 0.1 mol/L
3Check), filter cake ground 100 orders at 100 ℃ of lower dry 24h, placed 1mol/L (NH
4)
2S
2O
8Impregnation process in the solution (15 mL/g) is then filtered, oven dry, and 500 ℃ of roasting 5h obtain described S
2O
8 2-/ SnO
2-TiO
2Catalyst (Ti/ Sn mole proportioning is 1:3).
The Determination of Acidity of catalyst-1
Weighing 0.2g new controlling catalyst-1 is put into dry small test tube fast, adds 4～5 thionyl chlorides, then drips the benzole soln that 3～4 1g/ L contain DNFB (pKa=-14.52), and the sample surfaces its colour changed into yellow shows sample surfaces acid strength H
o≤-14.52, reach the super acids level.
The Determination of Acidity of catalyst-2
Weighing 0.2g new controlling catalyst-2 is put into dry small test tube fast, adds 4～5 thionyl chlorides, then drips the benzole soln that 3～4 1g/ L contain paranitrochlorobenzene (pKa=-12.70), and the sample surfaces its colour changed into yellow shows sample surfaces acid strength H
o≤-12.70, reach the super acids level.
The Determination of Acidity of catalyst-3
Weighing 0.2g new controlling catalyst-3 is put into dry small test tube fast, adds 4～5 thionyl chlorides, then drips the benzole soln that 3～4 1g/ L contain m-chloronitrobenzene (pKa=-13.16), and the sample surfaces its colour changed into yellow shows sample surfaces acid strength H
o≤-13.16, reach the super acids level.
The Determination of Acidity of catalyst-4
Quick weighing 0.2g new controlling catalyst-4, put into dry small test tube, add 4～5 thionyl chlorides, then drip the benzole soln that 3～4 1g/ L contain meta-nitrotoluene (pKa=-11.99), the sample surfaces its colour changed into yellow shows sample surfaces acid strength H
o≤-11.99, reach the super acids level.
The Determination of Acidity of catalyst-5
Weighing 0.2g new controlling catalyst-5 is put into dry small test tube fast, adds 4～5 thionyl chlorides, then drips the benzole soln that 3～4 1g/ L contain paranitrochlorobenzene (pKa=-12.70), and the sample surfaces its colour changed into yellow shows sample surfaces acid strength H
o≤-12.70, reach the super acids level.
Utilize catalyst-1 to carry out the waste sludge from paper mill cracking
Make moisture be lower than 5% waste sludge from paper mill (waste plastics) oven dry, pulverize, uniform feeding adds the fluidized bed cracking still, under the effect of catalyst-1(30%), 300 ℃ of cracking, catalytic pyrolysis 1 hour is squeezed into distillation still with the fuel oil component, collect respectively 40～190 ℃ and be the gasoline distillation stage, 250～330 ℃ is the diesel oil distillation stage.Going out oil recovery rate is 70%.HPLC detects purity and reaches 99.4%.
Utilize catalyst-2 to carry out the waste sludge from paper mill cracking
Make moisture be lower than 5% waste sludge from paper mill (waste plastics) oven dry, pulverize, uniform feeding adds the fluidized bed cracking still, under the effect of catalyst-2(1%), 500 ℃ of cracking, catalytic pyrolysis 10 hours is squeezed into distillation still with the fuel oil component, collect respectively 40～190 ℃ and be the gasoline distillation stage, 250～330 ℃ is the diesel oil distillation stage.Going out oil recovery rate is 75%.HPLC detects purity and reaches 99.6%.
Utilize catalyst-3 to carry out the waste sludge from paper mill cracking
Make moisture be lower than 5% waste sludge from paper mill (waste plastics) oven dry, pulverize, uniform feeding adds the fluidized bed cracking still, under the effect of catalyst-3(15%), 400 ℃ of cracking, catalytic pyrolysis 5 hours is squeezed into distillation still with the fuel oil component, collect respectively 40～190 ℃ and be the gasoline distillation stage, 250～330 ℃ is the diesel oil distillation stage.Going out oil recovery rate is 73%.HPLC detects purity and reaches 99.3%.
Utilize catalyst-4 to carry out the waste sludge from paper mill cracking
Make moisture be lower than 5% waste sludge from paper mill (waste plastics) oven dry, pulverize, uniform feeding adds the fluidized bed cracking still, under the effect of catalyst-4(30%), 350 ℃ of cracking, catalytic pyrolysis 5 hours is squeezed into distillation still with the fuel oil component, collect respectively 40～190 ℃ and be the gasoline distillation stage, 250～330 ℃ is the diesel oil distillation stage.Going out oil recovery rate is 76%.HPLC detects purity and reaches 99.7%.
Utilize catalyst-5 to carry out the waste sludge from paper mill cracking
Make moisture be lower than 5% waste sludge from paper mill (waste plastics) oven dry, pulverize, uniform feeding adds the fluidized bed cracking still, under the effect of catalyst-5(30%), 100 ℃ of cracking, catalytic pyrolysis 10 hours is squeezed into distillation still with the fuel oil component, collect respectively 40～190 ℃ and be the gasoline distillation stage, 250～330 ℃ is the diesel oil distillation stage.Going out oil recovery rate is 71%.HPLC detects purity and reaches 99.4%.
Solid super acid catalyst of the present invention: the mole of tin and transition metal all can be implemented in 2 ~ 20:1 scope.
Above-described embodiment is a kind of better scheme of the present invention, is not that the present invention is done any pro forma restriction, also has other variant and remodeling under the prerequisite that does not exceed the technical scheme that claim puts down in writing.
Claims (2)
1. waste plastics catalytic pyrolysis solid super acid catalyst, it is characterized in that: described solid super acid catalyst is that transition metal modified tin is solid super-strong acid, and the expression formula that described transition metal modified tin is solid super-strong acid is a kind of in the following formula: S
2O
8 2-/ SnO
2-Fe
2O
3, S
2O
8 2-/ SnO
2-ZnO, S
2O
8 2-/ SnO
2-TiO
2Described transition metal modified tin is that the mol ratio of tin and transition metal is 2 ~ 20:1 in the solid super-strong acid;
The waste plastics catalytic pyrolysis is as follows with preparation method's step of solid super acid catalyst:
1. with the soluble-salt of solubility pink salt and transition metal according to mole proportioning tin: the ratio of transition metal=2 ~ 20:1 is dissolved in the distilled water, mixes to get mixed liquor; The soluble-salt of transition metal is selected from a kind of in soluble ferric iron salt, soluble zinc salt, the solubility titanium salt, and described solubility pink salt is SnCl
45H
2O, described soluble ferric iron salt is FeCl
36H
2O, described soluble zinc salt are ZnCl
2, described solubility titanium salt is TiCl
4
2. add alkali lye in the mixed liquor that 1. obtains to step and regulate pH to 8 ~ 9, ageing 12 ~ 48h under the room temperature, suction filtration gets filter cake; Described alkali lye is concentrated ammonia liquor;
3. filter cake is after removal of impurities, oven dry, grinding, with (the NH of 1 ~ 2mol/L
4)
2S
2O
8Solution carries out impregnation process, after filtration, the drying, gets finished product after the roasting in air atmosphere; Described removal of impurities is for removing chlorion with filter cake with the washing of the ammonium acetate solution of mass concentration 2%, and described bake out temperature is that 100 ℃, time are 24h, after grinding 100 mesh sieves; Described sintering temperature is 500 ~ 600 ℃, and roasting time is 3 ~ 8h.
2. a waste plastics catalytic pyrolysis is applied to the processing of waste sludge from paper mill with solid super acid catalyst, and described application is specially following several:
One, make moisture be lower than 5% the waste sludge from paper mill oven dry, pulverize, uniform feeding adds the fluidized bed cracking still, at solid super acid catalyst S
2O
8 2-/ SnO
2-Fe
2O
3Effect is lower, and wherein Fe/ Sn mole proportioning is 1:9, and the solid super acid catalyst consumption is 30% of waste sludge from paper mill weight, 300 ℃ of cracking, catalytic pyrolysis 1 hour is squeezed into distillation still with the fuel oil component, collect respectively 40～190 ℃ and be the gasoline distillation stage, 250～330 ℃ is the diesel oil distillation stage; Going out oil recovery rate is that 70%, HPLC detection purity reaches 99.4%;
Two, make moisture be lower than 5% the waste sludge from paper mill oven dry, pulverize, uniform feeding adds the fluidized bed cracking still, at solid super acid catalyst S
2O
8 2-/ SnO
2-Fe
2O
3Effect is lower, and wherein Fe/ Sn mole proportioning is 1:6, and the solid super acid catalyst consumption is 15% of waste sludge from paper mill weight, 400 ℃ of cracking, catalytic pyrolysis 5 hours is squeezed into distillation still with the fuel oil component, collect respectively 40～190 ℃ and be the gasoline distillation stage, 250～330 ℃ is the diesel oil distillation stage; Going out oil recovery rate is that 73%, HPLC detection purity reaches 99.3%;
Three, make moisture be lower than 5% the waste sludge from paper mill oven dry, pulverize, uniform feeding adds the fluidized bed cracking still, at solid super acid catalyst S
2O
8 2-/ SnO
2-TiO
2Effect is lower, and wherein Ti/ Sn mole proportioning is 1:3, and the solid super acid catalyst consumption is 30% of waste sludge from paper mill weight, 100 ℃ of cracking, catalytic pyrolysis 10 hours is squeezed into distillation still with the fuel oil component, collect respectively 40～190 ℃ and be the gasoline distillation stage, 250～330 ℃ is the diesel oil distillation stage; Going out oil recovery rate is that 71%, HPLC detection purity reaches 99.4%.
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