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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- 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
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- 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
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- 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
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- 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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