CN105536818A - Preparation method for sulfonic acid type solid acid and method for utilizing waste plastic to prepare fuel oil - Google Patents
Preparation method for sulfonic acid type solid acid and method for utilizing waste plastic to prepare fuel oil Download PDFInfo
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- CN105536818A CN105536818A CN201610050274.0A CN201610050274A CN105536818A CN 105536818 A CN105536818 A CN 105536818A CN 201610050274 A CN201610050274 A CN 201610050274A CN 105536818 A CN105536818 A CN 105536818A
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- 239000011973 solid acid Substances 0.000 title claims abstract description 47
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000004033 plastic Substances 0.000 title claims abstract description 29
- 229920003023 plastic Polymers 0.000 title claims abstract description 29
- 239000002699 waste material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000295 fuel oil Substances 0.000 title claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 238000005336 cracking Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 10
- 235000009566 rice Nutrition 0.000 claims abstract description 10
- 238000004821 distillation Methods 0.000 claims abstract description 9
- 239000006166 lysate Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006277 sulfonation reaction Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000010903 husk Substances 0.000 claims description 10
- 241000209094 Oryza Species 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 9
- 239000002283 diesel fuel Substances 0.000 claims description 8
- 239000003502 gasoline Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000011002 quantification Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- 240000007594 Oryza sativa Species 0.000 abstract 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 3
- 229910001626 barium chloride Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- UEUIKXVPXLWUDU-UHFFFAOYSA-O 4-sulfobenzenediazonium Chemical compound OS(=O)(=O)C1=CC=C([N+]#N)C=C1 UEUIKXVPXLWUDU-UHFFFAOYSA-O 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000012962 cracking technique Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/086—Characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a preparation method for sulfonic acid type solid acid. Rice hulls are used as carbon sources, treated for 1-5 h in a hydrofluoric acid solution with the mass concentration being 30% at the temperature of 25 DEG C-30 DEG C, carbonized for 0.5-3 h in concentrated sulfuric acid at the temperature of 50 DEG C-100 DEG C, and then sulphonated for 1-3 h in fuming sulfuric acid at the temperature of 100 DEG C-150 DEG C to obtain sulfonic acid type solid acid, and catalytic performance of sulfonic acid type solid acid is good. The invention further discloses a method for utilizing waste plastic to prepare fuel oil with obtained sulfonic acid type solid acid as a catalyst. The method comprises the steps of waste plastic washing, drying and smashing pretreatment to obtain smashed raw materials; putting the smashed raw materials and sulfonic acid type solid acid into a splitting container, and enabling the smashed raw materials and sulfonic acid type solid acid to be subjected to a cracking reaction for 1-5 h at the temperature of 300 DEG C-500 DEG C; putting lysate into a distillation container, enabling lysate to be treated in a distilled mode, and collecting fraction with the temperature being 40 DEG C-330 DEG C. No solid waste is generated, and the method is environmentally friendly.
Description
Technical field
The present invention relates to a kind of waste plastics recovery and utilize technology, especially a kind ofly novel carbon back sulfonic acid type solid acid is applied as catalyst, utilize cracking technique to prepare the green process technology of fuel oil, also relates to the preparation method of carbon back sulfonic acid type solid acid used simultaneously.
Background technology
In recent years, plastics industry sustainable development, the ratio of scrapped plastic products shared by industry and sanitary waste was increasing, and the impact caused to environmental sanitation is also more and more serious.Rising steadily particularly along with petroleum-based energy goods processing charges, the recycling of waste or used plastics has become very urgent and necessary as protection of the environment and energy-saving and emission-reduction measure, is the important directions solving recycling economy development from now on.
Also showing great attention to of people is received as the application of Green Chemical Technology at chemical field solid acid.Utilize solid acid as heterogeneous catalysis, generally have not etching apparatus, pollute little, high temperature resistant, post processing is simple, easily separated and low cost and other advantages, and obtains extensive investigation and application in acid catalysis field.Carbon back sulfonic acid type solid acid is the important solid acid of a class that development in recent years is got up, is utilize living beings to control to carbonize the solid sulfoacid prepared.Therefore, new and effective carbon back sulfonic acid type solid acid is used for used plastics oil tech as catalyst to have great significance.
At present, the preparation method of sulfonic acid type solid acid mainly contains three kinds: the carbon source that sucrose, glucose etc. are easily polymerized by (1) and the common hot step of the concentrated sulfuric acid complete and carbonize and sulfonation, obtain the sulfonic acid type solid acid catalyst with macroporous structure.The sulfonic acid type solid acid catalyst poor stability that this method is obtained, in the liquid-phase reaction system that temperature is higher, acidic-group easily comes off, and causes catalyst activity reduction or inactivation.(2) first the carbon sources such as sucrose, glucose, coconut husk, bamboo bits carbonized, then obtain sulfonic acid type solid acid with the concentrated sulfuric acid or oleum sulfonation, sulfonic acid type solid acid specific area prepared by this method is low, affects its catalytic performance and range of application.(3) with to diazo benzene sulfonic acid for sulfonated reagent, sulfonation has the material with carbon element enriching pore structure and bigger serface and prepares sulfonic acid type solid acid.The reaction condition of this method is gentle, and the acid amount of obtained sulfonic acid type solid acid is high, and specific area is large, but diazobenzene sulfonate is expensive, is unfavorable for suitability for industrialized production.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of preparation method of novel carbon back sulfonic acid type solid acid, and realizes as catalyst the new technology that waste plastics catalyse pyrolysis prepares fuel oil with gained carbon back sulfonic acid type solid acid.
For solving above technical problem, first the present invention discloses a kind of preparation method of sulfonic acid type solid acid, this preparation method take rice husk as carbon source, at prior to 25 ~ 30 DEG C mass concentration be in the hydrofluoric acid solution of 30% process 1 ~ 5 hour, carbonization 0.5 ~ 3 hour in concentrated sulfuric acid at 50 ~ 100 DEG C again, then at 100 ~ 150 DEG C, in oleum, sulfonation obtains sulfonic acid type solid acid in 1 ~ 3 hour.
Further, this preparation method comprises the steps:
(1), carbonization process: get quantitative dry rice husk, at 25 ~ 30 DEG C, be soak 1 ~ 5 hour in the hydrofluoric acid solution of 30% in mass concentration, after suction filtration, washing, naturally drying, at 50 ~ 100 DEG C, carbonization obtains carbide in 0.5 ~ 3 hour in concentrated sulfuric acid, this carbide is again after cooling, filtering, spend deionized water to neutral, after drying, obtain carbide after drying, for subsequent use;
(2), sulfonation process: get quantification steps (1) gained carbide after drying, add SO
3mass fraction is in the oleum of 50%, is warming up to 100 ~ 150 DEG C and constant temperature sulfonation 1 ~ 5 hour, adds deionized water cooling cessation reaction, filters, get Washing of Filter Cake to sulfate radical-free ion, obtain object sulfonic acid type solid acid after drying.
Further, described in step (1), the quality amount ratio of dry rice husk and the concentrated sulfuric acid is 1:1 ~ 5.
Further, the quality amount ratio of carbide after drying described in step (2) and oleum is 1:1 ~ 3.
The invention also discloses one utilizes waste plastic for raw material, and with the method that the sulfonic acid type solid acid that preceding method prepares is catalyst preparing fuel oil, the method comprises the steps:
(1), by waste plastics after washing, oven dry, comminution pretreatment, the raw material after pulverizing is obtained;
(2), by the raw material after pulverizing and drop in cracking container according to the sulfonic acid type solid acid that aforementioned open method prepares, cracking reaction 1 ~ 5 hour at 300 ~ 500 DEG C of temperature;
(3), by lysate squeeze in distil container and carry out distillation process, collect the cut of 40 ~ 330 DEG C.
Further, in described step (2), cracking reaction 2 ~ 3 hours at 350 ~ 450 DEG C of temperature.
Further, in described step (3), collect the cut of 40 ~ 190 DEG C as gasoline, collect the cut of 250 ~ 330 DEG C as diesel oil.
Further, the quality that feeds intake of sulfonic acid type solid acid described in step (2) is 5 ~ 30% of the quality that feeds intake of pretreated waste plastics in step (1).
Further, in step (1) waste plastics through washing, dry, comminution pretreatment is specially and first waste plastics washed away dust, to dry to moisture lower than 5%, then pulverize.
Compared with prior art, the method utilizing sulfonic acid type solid acid catalyst to produce fuel oil of the present invention generates without solid waste, environmental friendliness, gained fuel oil purity is high, and the inventive method is suitable for the suitability for industrialized production of certain scale, be a green clearer production technology of turning waste into wealth, not yet have the application report of suitability for industrialized production at present.The present invention additionally uses the method preparing sulfonic acid type solid acid that is different from prior art, and raw material is easy to get, and cost is low, and gained sulfonic acid type solid acid catalysis excellent performance, content is high, and repeat performance is good.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
the preparation of catalyst
embodiment 1
1, carbonization process: by 100 grams, dry rice husk in the hydrofluoric acid solution 500 grams of mass concentration 30%, 25 DEG C are soaked 5 hours, use Buchner funnel suction filtration, after clear water washing, naturally dry.Then add the concentrated sulfuric acid 500 grams, 50 DEG C of charings 3 hours, Temperature fall, to room temperature (25 DEG C), filtered, and carbide spends deionized water to neutral, obtains carbide after drying after drying, for subsequent use.
2, sulfonation process: get above-mentioned 10 grams, carbide after drying, add SO
3the oleum of mass fraction 50% 30 grams, be warming up to 100 DEG C of constant temperature sulfonation 2 hours, add deionized water cooling cessation reaction, filter, solids spends deionized water and detects to sulfate radical-free ion to barium chloride solution, obtain sulfonic acid type solid acid catalyst 11 grams after drying, acid content is 2.01mmol/g, purity 99.8%.
embodiment 2
1, carbonization process: by 100 grams, dry rice husk in the hydrofluoric acid solution 500 grams of mass concentration 30%, 25 DEG C are soaked 1 hour, use Buchner funnel suction filtration, after clear water washing, naturally dry.Then add the concentrated sulfuric acid 100 grams, 100 DEG C of charings 1 hour, Temperature fall, to room temperature (25 DEG C), filtered, and carbide spends deionized water to neutral, obtains carbide after drying after drying, for subsequent use.
2, sulfonation process: get 10 grams, above-mentioned dried carbide, add SO
3the oleum of mass fraction 50% 10 grams, be warming up to 150 DEG C of constant temperature sulfonation 3 hours, add deionized water cooling cessation reaction, filter, solids spends deionized water and detects to sulfate radical-free ion to barium chloride solution, obtain sulfonic acid type solid acid catalyst 11.2 grams after drying, acid content is 2.03mmol/g, purity 99.8%.
embodiment 3
1, carbonization process: by 100 grams, dry rice husk in the hydrofluoric acid solution 500 grams of mass concentration 30%, 30 DEG C are soaked 3 hours, use Buchner funnel suction filtration, after clear water washing, naturally dry.Then add the concentrated sulfuric acid 300 grams, 80 DEG C of charings 3 hours, Temperature fall, to room temperature (25 DEG C), filtered, and carbide spends deionized water to neutral, obtains carbide after drying after drying, for subsequent use.
2, sulfonation process: get 10 grams, above-mentioned dried carbide, add SO
3the oleum of mass fraction 50% 20 grams, be warming up to 120 DEG C of constant temperature sulfonation 2 hours, add deionized water cooling cessation reaction, filter, solids spends deionized water and detects to sulfate radical-free ion to barium chloride solution, obtain sulfonic acid type solid acid catalyst 11.1 grams after drying, acid content is 2.01mmol/g, purity 99.8%.
embodiment 4: cracking waste plastics prepares fuel oil
After dust is removed in waste plastics washing, oven dry makes biodiversity content lower than 5%, pulverize, the sulfonic acid type solid acid catalyst 30 grams getting the raw material after pulverizing 100 grams and embodiment 1 preparation mixes, and adds fluidized bed cracking still (conventional closed reactor), after charging, 300 DEG C of cracking 1 hour, after reaction terminates, lysate is squeezed into distillation still (conventional distil-lation still), collect 40 ~ 190 DEG C of effluxes respectively as gasoline, 250 ~ 330 DEG C of cuts are as diesel oil.Going out oil recovery rate is 70%.HPLC detects, and the purity of gasoline and diesel oil all reaches 99.4%.
embodiment 5: cracking waste plastics prepares fuel oil
After dust is removed in waste plastics washing, oven dry makes biodiversity content lower than 5%, pulverize, the sulfonic acid type solid acid catalyst 20 grams getting the raw material after pulverizing 100 grams and embodiment 2 preparation mixes, and adds fluidized bed cracking still (conventional closed reactor), after charging, 400 DEG C of cracking 3 hours, after reaction terminates, lysate is squeezed into distillation still (conventional distil-lation still), collect 40 ~ 190 DEG C of effluxes respectively as gasoline, 250 ~ 330 DEG C of cuts are as diesel oil.Going out oil recovery rate is 70%.HPLC detects, and the purity of gasoline and diesel oil all reaches 99.4%.
embodiment 6: utilize embodiment 3 catalyst to carry out waste sludge from paper mill cracking
After dust is removed in waste plastics washing, oven dry makes biodiversity content lower than 5%, pulverize, the sulfonic acid type solid acid catalyst 10 grams getting the raw material after pulverizing 100 grams and embodiment 3 preparation mixes, and adds fluidized bed cracking still (conventional closed reactor), after charging, 500 DEG C of cracking 1 hour, after reaction terminates, lysate is squeezed into distillation still (conventional distil-lation still), collect 40 ~ 190 DEG C of effluxes respectively as gasoline, 250 ~ 330 DEG C of cuts are as diesel oil.Going out oil recovery rate is 70%.HPLC detects, and the purity of gasoline and diesel oil all reaches 99.4%.
Claims (9)
1. the preparation method of a sulfonic acid type solid acid, it is characterized in that: this preparation method take rice husk as carbon source, at prior to 25 ~ 30 DEG C mass concentration be in the hydrofluoric acid solution of 30% process 1 ~ 5 hour, carbonization 0.5 ~ 3 hour in concentrated sulfuric acid at 50 ~ 100 DEG C again, then at 100 ~ 150 DEG C, in oleum, sulfonation obtains sulfonic acid type solid acid in 1 ~ 3 hour.
2. the preparation method of sulfonic acid type solid acid according to claim 1, is characterized in that this preparation method comprises the steps:
(1), carbonization process: get quantitative dry rice husk, at 25 ~ 30 DEG C, be soak 1 ~ 5 hour in the hydrofluoric acid solution of 30% in mass concentration, after suction filtration, washing, naturally drying, at 50 ~ 100 DEG C, carbonization obtains carbide in 0.5 ~ 3 hour in concentrated sulfuric acid, this carbide is again after cooling, filtering, spend deionized water to neutral, after drying, obtain carbide after drying, for subsequent use;
(2), sulfonation process: get quantification steps (1) gained carbide after drying, add SO
3mass fraction is in the oleum of 50%, is warming up to 100 ~ 150 DEG C and constant temperature sulfonation 1 ~ 5 hour, adds deionized water cooling cessation reaction, filters, get Washing of Filter Cake to sulfate radical-free ion, obtain object sulfonic acid type solid acid after drying.
3. the preparation method of sulfonic acid type solid acid according to claim 2, is characterized in that: described in step (1), the quality amount ratio of dry rice husk and the concentrated sulfuric acid is 1:1 ~ 5.
4. the preparation method of sulfonic acid type solid acid according to claim 2, is characterized in that: the quality amount ratio of carbide after drying described in step (2) and oleum is 1:1 ~ 3.
5. utilize waste plastic to prepare a method for fuel oil, it is characterized in that the method comprises the steps:
(1), by waste plastics after washing, oven dry, comminution pretreatment, the raw material after pulverizing is obtained;
(2), the raw material after pulverizing and the sulfonic acid type solid acid for preparing according to method described in claim 1-4 any one claim are dropped in cracking container, cracking reaction 1 ~ 5 hour at 300 ~ 500 DEG C of temperature;
(3), by lysate squeeze in distil container and carry out distillation process, collect the cut of 40 ~ 330 DEG C.
6. utilize waste plastic to prepare the method for fuel oil according to claim 5, it is characterized in that: in described step (2), cracking reaction 2 ~ 3 hours at 350 ~ 450 DEG C of temperature.
7. utilize waste plastic to prepare the method for fuel oil according to claim 5, it is characterized in that: in described step (3), collect the cut of 40 ~ 190 DEG C as gasoline, collect the cut of 250 ~ 330 DEG C as diesel oil.
8. utilize waste plastic to prepare the method for fuel oil according to claim 5, it is characterized in that: the quality that feeds intake of sulfonic acid type solid acid described in step (2) is 5 ~ 30% of the quality that feeds intake of pretreated waste plastics in step (1).
9. utilize waste plastic to prepare the method for fuel oil according to claim 5, it is characterized in that: in step (1), waste plastics is specially first waste plastics is washed away dust through washing, oven dry, comminution pretreatment, oven dry, is then pulverized to moisture lower than 5%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117380273A (en) * | 2022-07-04 | 2024-01-12 | 中国科学院广州能源研究所 | A plastic-based solid acid catalyst and its method for directional catalytic depolymerization of biomass |
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| KR100896428B1 (en) * | 2007-11-12 | 2009-05-12 | 한국에너지기술연구원 | Method for preparing organic polymer and solid acid catalyst for heavy oil pyrolysis using oil shale pyrolysis residue and light oil obtaining method using same |
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