CN102888240B - Method for preparing high-performance fuel oil by adopting mesoporous alkaline carbon materials to carry out catalytic cracking on grease - Google Patents
Method for preparing high-performance fuel oil by adopting mesoporous alkaline carbon materials to carry out catalytic cracking on grease Download PDFInfo
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- CN102888240B CN102888240B CN201210411843.1A CN201210411843A CN102888240B CN 102888240 B CN102888240 B CN 102888240B CN 201210411843 A CN201210411843 A CN 201210411843A CN 102888240 B CN102888240 B CN 102888240B
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000000295 fuel oil Substances 0.000 title claims abstract description 11
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 9
- 239000004519 grease Substances 0.000 title abstract description 5
- 238000004523 catalytic cracking Methods 0.000 title abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 48
- 238000003763 carbonization Methods 0.000 claims description 38
- 239000012153 distilled water Substances 0.000 claims description 36
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 36
- 239000010931 gold Substances 0.000 claims description 36
- 229910052737 gold Inorganic materials 0.000 claims description 36
- 229930006000 Sucrose Natural products 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 239000003921 oil Substances 0.000 claims description 26
- 239000005720 sucrose Substances 0.000 claims description 26
- 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 claims description 25
- 238000005336 cracking Methods 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000002808 molecular sieve Substances 0.000 claims description 13
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 13
- 239000000969 carrier Substances 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 12
- 230000008020 evaporation Effects 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 12
- 238000002390 rotary evaporation Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 11
- 238000007233 catalytic pyrolysis Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 6
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000013335 mesoporous material Substances 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 13
- 235000015320 potassium carbonate Nutrition 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 239000002283 diesel fuel Substances 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001342 alkaline earth metals Chemical class 0.000 description 4
- 229910052728 basic metal Inorganic materials 0.000 description 4
- 150000003818 basic metals Chemical class 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 235000019484 Rapeseed oil Nutrition 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- WJEIYVAPNMUNIU-UHFFFAOYSA-N [Na].OC(O)=O Chemical compound [Na].OC(O)=O WJEIYVAPNMUNIU-UHFFFAOYSA-N 0.000 description 2
- 239000008157 edible vegetable oil Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000009656 pre-carbonization Methods 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000000185 sucrose group Chemical group 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing high-performance fuel oil by adopting mesoporous alkaline carbon materials to carry out catalytic cracking on grease. The method comprises the following steps of: synthesizing a mesoporous carbon carrier by virtue of a hard template method, and loading hydroxide of alkali or carbonate accounting for 1%-15% of the mass of the mesoporous carbon carrier on the surface of the mesoporous carbon carrier to obtain an alkaline mesoporous carbon catalyst; and weighing triglyceride and the catalyst according to a mass ratio of m triglyceride to m alkaline mesoporous carbon catalyst equal to 100: (1-10), putting the triglyceride and the catalyst into a reaction kettle, heating the reaction kettle to 350-500 DEG C, and collecting generated fraction to obtain a dark brown liquid, namely the product. The carbon material is an inert material and can well keep an original mesoporous structure after being loaded. As the alkaline catalyst and the mesoporous material carrier are matched with each other, not only can low-acid-value catalytic cracking liquid fuel oil with less content of carboxyl be obtained, but also the molecular weight distribution of split products can be controlled so as to obtain diesel fractions (C14-C22) in a directional way.
Description
Technical field
The invention belongs to biomass energy transformation technology field, relate generally to a kind of research of new triglyceride level catalytic cracking catalyst.
Background technology
Take oil, coal is that main primary energy source is just day by day exhausted, and biomass energy is to utilize organic substance renewable or circulation, comprises that farm crop, trees and other plant and residual body thereof etc. be raw material, carries out the industry of bio-based product, biofuel production.By triglyceride level catalytic pyrolysis, be wherein a kind of effective ways of prepare liquid fuel.In patent before (200910029495.X) we the reaction of oil splitting under base catalysis effect has been described, but owing to only adopting basic cpd as catalyzer, the molecular weight distribution of split product is wider, what part material occurred is random pyrolytic reaction, further generate low-carbon (LC) hydro carbons, yield is reduced.For improving oil product yield, be mainly the yield that improves diesel oil distillate, we wish to adopt mesoporous carrier, utilize its aperture structure (>2nm, the catalyzer of general micropore easily forms low-carbon (LC) hydro carbons), reduce the generation of second pyrolysis reaction.Once used multiple mesoporous silicon as carrier, but mesoporous silicon material recurring structure unstability very easily under strong alkaline condition, the general catalyzer that cannot obtain regular meso-hole structure after load (New Type of Mesoporous solid alkali material synthetic. chemical progress. 2009,21:1839-1846).
Summary of the invention
the technical problem solving:in order to solve existing catalyzer as the problem of mesoporous silicon material pore structure unstability under alkaline condition, the invention provides a kind of preparation method of mesoporous alkaline carbon material, high with this cracking catalyst grease yield, the cracked oil molecular weight product obtaining concentrates on diesel oil distillate (C14-C22).
technical scheme:a method for mesoporous alkaline carbon material catalytic pyrolysis oil and fat preparation high-performance fuel oil, comprises the following steps:
The first step, adopts the synthesising mesoporous carbon support of hard template method, and will account for the basic metal of mesoporous carrier quality 1%-15%, the oxyhydroxide of alkaline-earth metal or carbonate are carried on mesoporous carbon carrier surface, obtains alkaline gold/mesoporous carbon catalyst;
Second step, in mass ratio m
triglyceride level: m
alkalescence gold/mesoporous carbon catalystthe ratio of=100:1～10, takes triglyceride, alkaline gold/mesoporous carbon catalyst is put into reactor, and the cut producing is collected in reacting by heating still to 350～500 ℃, obtains dark-brown liquid and is product.
Hard mould agent in described hard template method is selected SBA-15, carbon source is sucrose, through pre-carbonization and carbonization, form carbon-silicon compound, with the HF aqueous solution, remove silicon template afterwards, obtain mesoporous carbon carrier, and the oxyhydroxide of the basic metal of 1%-15%wt, alkaline-earth metal or carbonate are carried on to carrier surface, obtain alkaline gold/mesoporous carbon catalyst.
Described alkali-metal oxyhydroxide is sodium hydroxide or potassium hydroxide, and alkali-metal carbonate is sodium carbonate or salt of wormwood.
Described triglyceride level is any one in soybean oil, rapeseed oil, sewer oil or used edible oil.
beneficial effect:alkaline gold/mesoporous carbon catalyst of the present invention, tool has the following advantages:
1. carbon material is inert material, after overload, can keep well original meso-hole structure, and conventional silicon type mesoporous material is unstable under alkaline condition, cannot obtain the alkaline mesoporous catalyst that pore structure is stable.
2. adopt basic catalyst and mesoporous material carrier to cooperatively interact, not only can obtain the less low acid value catalytic pyrolysis liquid fuel oil of carboxyl-content, can also control the molecular weight distribution of split product, orientation obtains diesel oil distillate (C14-C22), as shown in Figure 1.
3. the basic cpd that load is used is simple and easy to get, and carrying method is simple.
4. the method adaptability to raw material is wide, can process all kinds of different greases, comprises the more unmanageable raw materials such as waste grease, acidifying grease.
Accompanying drawing explanation
The cracked oil product gas chromatogram that Fig. 1 different catalysts produces (a. alkalescence gold/mesoporous carbon catalyst, b. sodium carbonate catalyst);
The fuel oil product of preparing gained by alkaline gold/mesoporous carbon catalyst, can orientation obtain diesel oil distillate (C14-C22), and area normalization method calculates gained content >70 %.And the distribution of general alkali catalyzer carbonic acid sodium molecule amount disperses, the content < 50% of diesel oil distillate (C14-C22).
The cracked oil product molecular weight distribution that Fig. 2 different catalysts produces (a. alkalescence gold/mesoporous carbon catalyst, b. sodium carbonate catalyst).
By molecular weight distribution determination, can obviously find, alkalescence gold/mesoporous carbon catalyst is prepared the fuel oil product of gained, its molecular weight distribution has stronger peak value at 280-320, and the fuel oil product molecular weight distribution of general alkali catalyzer carbonic acid sodium gained is lower, the structure regulating effect that meso-hole structure plays is described
Embodiment
Experiment is commercially available with soybean oil, rapeseed oil, sewer oil and used edible oil.
A method for mesoporous alkaline carbon material catalytic pyrolysis oil and fat preparation high-performance fuel oil, comprises the following steps:
The first step, adopts the synthesising mesoporous carbon support of hard template method, and the oxyhydroxide of the basic metal of 1%-15%wt, alkaline-earth metal, carbonate is carried on to carrier surface, obtains alkaline gold/mesoporous carbon catalyst; Described hard mould agent is SBA-15 mesopore molecular sieve, and sucrose is carbon source, through 160 ℃ of pre-carbonizations and 900 ℃ of carbonizations, obtains mesoporous carbon carrier; Described basic metal or the oxyhydroxide of alkaline-earth metal or carbonate are any one in sodium hydroxide, sodium carbonate, potassium hydroxide, salt of wormwood, preferential oxidation sodium.
Second step, in mass ratio m
triglyceride level: m
alkalescence gold/mesoporous carbon catalystthe ratio of=100:1～10, takes triglyceride, alkaline gold/mesoporous carbon catalyst is put into reactor, and the cut producing is collected in reacting by heating still to 350～500 ℃, obtains dark-brown liquid and is product.
Wherein, mesoporous carbon carrier preparation method is:
1) mesoporous molecular sieve SBA-15 of 1 g (hard mould agent) is dissolved in the distilled water of 11 mL, adds the sucrose of 1.25 g and the sulfuric acid of 7.2 mL 0.2 mol/L, ultrasonic 1 h;
2) under the condition of 90 ℃, moisture is evaporated to constant weight, then at 160 ℃ preliminary carbonization 6 h;
3) product of preliminary carbonization was ground to 80 mesh sieves, then be dissolved in 11 mL water, again added the sucrose of 0.75 g and the sulfuric acid of 4 mL 0.2 mol/L;
4) repeat the process of 90 ℃ of moisture evaporations and 160 ℃ of preliminary carbonizations;
5) at N
2protection under, put into 900 ℃, tube furnace insulation, 5 h;
6) to be dissolved in volume fraction be that 5% HF solution stirring, 24 h remove hard mould agents to products therefrom;
7) centrifugal, with distilled water, be washed till neutrality, be put in 60 ℃ of dry mesoporous carbon carriers that obtain in baking oven.
Alkalescence gold/mesoporous carbon catalyst preparation method:
1) 0.05 g salt of wormwood is dissolved in to 10 mL distilled water;
2) add 1 g mesoporous carbon carrier, ultrasonic 1 h;
3) rotary evaporation is removed moisture, obtains alkaline gold/mesoporous carbon catalyst (5 %wt salt of wormwood).
embodiment 1:
The mesoporous molecular sieve SBA-15 of 1 g (hard mould agent) is dissolved in the distilled water of 11 mL, adds the sucrose of 1.25 g and the sulfuric acid of 7.2 mL 0.2 mol/L, ultrasonic 1 h; Under the condition of 90 ℃, moisture is evaporated to constant weight, then at 160 ℃ preliminary carbonization 6 h; The product of preliminary carbonization was ground to 80 mesh sieves, then be dissolved in 11 mL water, again added the sucrose of 0.75 g and the sulfuric acid of 4 mL 0.2 mol/L; Repeat the process of 90 ℃ of moisture evaporations and 160 ℃ of preliminary carbonizations; At N
2protection under, put into 900 ℃, tube furnace insulation, 5 h; It is that 5% HF solution stirring, 24 h remove hard mould agents that products therefrom is dissolved in volume fraction; Centrifugal, with distilled water, be washed till neutrality, be put in 60 ℃ of dry mesoporous carbon carriers that obtain in baking oven.0.05 g salt of wormwood is dissolved in to 10 mL distilled water; Add 1 g mesoporous carbon carrier, ultrasonic 1 h; Rotary evaporation is removed moisture, obtains alkaline gold/mesoporous carbon catalyst (5 %wt salt of wormwood).10 g soybean oil, 0.5 g alkalescence gold/mesoporous carbon catalyst (5 %wt salt of wormwood) are added to cracking tube.Be warming up to 420 ℃, occur that condensed fluid is to generating without cut.Cracking obtains liquid 7.8 g, carbon residue 0.7 g, non-condensable gases 1.5 g.
embodiment 2:
The mesoporous molecular sieve SBA-15 of 1 g (hard mould agent) is dissolved in the distilled water of 11 mL, adds the sucrose of 1.25 g and the sulfuric acid of 7.2 mL 0.2 mol/L, ultrasonic 1 h; Under the condition of 90 ℃, moisture is evaporated to constant weight, then at 160 ℃ preliminary carbonization 6 h; The product of preliminary carbonization was ground to 80 mesh sieves, then be dissolved in 11 mL water, again added the sucrose of 0.75 g and the sulfuric acid of 4 mL 0.2 mol/L; Repeat the process of 90 ℃ of moisture evaporations and 160 ℃ of preliminary carbonizations; At N
2protection under, put into 900 ℃, tube furnace insulation, 5 h; It is that 5% HF solution stirring, 24 h remove hard mould agents that products therefrom is dissolved in volume fraction; Centrifugal, with distilled water, be washed till neutrality, be put in 60 ℃ of dry mesoporous carbon carriers that obtain in baking oven.0.05 g salt of wormwood is dissolved in to 10 mL distilled water; Add 1 g mesoporous carbon carrier, ultrasonic 1 h; Rotary evaporation is removed moisture, obtains alkaline gold/mesoporous carbon catalyst (5 %wt salt of wormwood).10 g rapeseed oils, 0.5 g alkalescence gold/mesoporous carbon catalyst (5 %wt salt of wormwood) are added to cracking tube.Be warming up to 420 ℃, occur that condensed fluid is to generating without cut.Cracking obtains liquid 7.7 g, carbon residue 0.7 g, non-condensable gases 1.6 g.
embodiment 3:
The mesoporous molecular sieve SBA-15 of 1 g (hard mould agent) is dissolved in the distilled water of 11 mL, adds the sucrose of 1.25 g and the sulfuric acid of 7.2 mL 0.2 mol/L, ultrasonic 1 h; Under the condition of 90 ℃, moisture is evaporated to constant weight, then at 160 ℃ preliminary carbonization 6 h; The product of preliminary carbonization was ground to 80 mesh sieves, then be dissolved in 11 mL water, again added the sucrose of 0.75 g and the sulfuric acid of 4 mL 0.2 mol/L; Repeat the process of 90 ℃ of moisture evaporations and 160 ℃ of preliminary carbonizations; At N
2protection under, put into 900 ℃, tube furnace insulation, 5 h; It is that 5% HF solution stirring, 24 h remove hard mould agents that products therefrom is dissolved in volume fraction; Centrifugal, with distilled water, be washed till neutrality, be put in 60 ℃ of dry mesoporous carbon carriers that obtain in baking oven.0.05 g salt of wormwood is dissolved in to 10 mL distilled water; Add 1 g mesoporous carbon carrier, ultrasonic 1 h; Rotary evaporation is removed moisture, obtains alkaline gold/mesoporous carbon catalyst (5 %wt salt of wormwood).10 g sewer oils, 0.5 g alkalescence gold/mesoporous carbon catalyst (5 %wt salt of wormwood) are added to cracking tube.Be warming up to 420 ℃, occur that condensed fluid is to generating without cut.Cracking obtains liquid 7.4 g, carbon residue 1.7 g, non-condensable gases 0.9 g.
embodiment 4:
The mesoporous molecular sieve SBA-15 of 1 g (hard mould agent) is dissolved in the distilled water of 11 mL, adds the sucrose of 1.25 g and the sulfuric acid of 7.2 mL 0.2 mol/L, ultrasonic 1 h; Under the condition of 90 ℃, moisture is evaporated to constant weight, then at 160 ℃ preliminary carbonization 6 h; The product of preliminary carbonization was ground to 80 mesh sieves, then be dissolved in 11 mL water, again added the sucrose of 0.75 g and the sulfuric acid of 4 mL 0.2 mol/L; Repeat the process of 90 ℃ of moisture evaporations and 160 ℃ of preliminary carbonizations; At N
2protection under, put into 900 ℃, tube furnace insulation, 5 h; It is that 5% HF solution stirring, 24 h remove hard mould agents that products therefrom is dissolved in volume fraction; Centrifugal, with distilled water, be washed till neutrality, be put in 60 ℃ of dry mesoporous carbon carriers that obtain in baking oven.0.05 g potassium hydroxide is dissolved in to 10 mL distilled water; Add 1 g mesoporous carbon carrier, ultrasonic 1 h; Rotary evaporation is removed moisture, obtains alkaline gold/mesoporous carbon catalyst (5 %wt potassium hydroxide).10 g sewer oils, 0.5 g alkalescence gold/mesoporous carbon catalyst (5 %wt potassium hydroxide) are added to cracking tube.Be warming up to 420 ℃, occur that condensed fluid is to generating without cut.Cracking obtains liquid 7.3 g, carbon residue 1.8 g, non-condensable gases 0.9 g.
embodiment 5:
The mesoporous molecular sieve SBA-15 of 1 g (hard mould agent) is dissolved in the distilled water of 11 mL, adds the sucrose of 1.25 g and the sulfuric acid of 7.2 mL 0.2 mol/L, ultrasonic 1 h; Under the condition of 90 ℃, moisture is evaporated to constant weight, then at 160 ℃ preliminary carbonization 6 h; The product of preliminary carbonization was ground to 80 mesh sieves, then be dissolved in 11 mL water, again added the sucrose of 0.75 g and the sulfuric acid of 4 mL 0.2 mol/L; Repeat the process of 90 ℃ of moisture evaporations and 160 ℃ of preliminary carbonizations; At N
2protection under, put into 900 ℃, tube furnace insulation, 5 h; It is that 5% HF solution stirring, 24 h remove hard mould agents that products therefrom is dissolved in volume fraction; Centrifugal, with distilled water, be washed till neutrality, be put in 60 ℃ of dry mesoporous carbon carriers that obtain in baking oven.0.05 g sodium carbonate is dissolved in to 10 mL distilled water; Add 1 g mesoporous carbon carrier, ultrasonic 1 h; Rotary evaporation is removed moisture, obtains alkaline gold/mesoporous carbon catalyst (5 %wt sodium carbonate).10 g sewer oils, 0.5 g alkalescence gold/mesoporous carbon catalyst (5 %wt sodium carbonate) are added to cracking tube.Be warming up to 420 ℃, occur that condensed fluid is to generating without cut.Cracking obtains liquid 7.1 g, carbon residue 1.9 g, non-condensable gases 1.0 g.
embodiment 6:
The mesoporous molecular sieve SBA-15 of 1 g (hard mould agent) is dissolved in the distilled water of 11 mL, adds the sucrose of 1.25 g and the sulfuric acid of 7.2 mL 0.2 mol/L, ultrasonic 1 h; Under the condition of 90 ℃, moisture is evaporated to constant weight, then at 160 ℃ preliminary carbonization 6 h; The product of preliminary carbonization was ground to 80 mesh sieves, then be dissolved in 11 mL water, again added the sucrose of 0.75 g and the sulfuric acid of 4 mL 0.2 mol/L; Repeat the process of 90 ℃ of moisture evaporations and 160 ℃ of preliminary carbonizations; At N
2protection under, put into 900 ℃, tube furnace insulation, 5 h; It is that 5% HF solution stirring, 24 h remove hard mould agents that products therefrom is dissolved in volume fraction; Centrifugal, with distilled water, be washed till neutrality, be put in 60 ℃ of dry mesoporous carbon carriers that obtain in baking oven.By 0.05 g dissolution of sodium hydroxide in 10 mL distilled water; Add 1 g mesoporous carbon carrier, ultrasonic 1 h; Rotary evaporation is removed moisture, obtains alkaline gold/mesoporous carbon catalyst (5 %wt sodium hydroxide).10 g sewer oils, 0.5 g alkalescence gold/mesoporous carbon catalyst (5 %wt sodium hydroxide) are added to cracking tube.Be warming up to 420 ℃, occur that condensed fluid is to generating without cut.Cracking obtains liquid 7.2 g, carbon residue 1.7 g, non-condensable gases 1.1 g.
embodiment 7:
The mesoporous molecular sieve SBA-15 of 1 g (hard mould agent) is dissolved in the distilled water of 11 mL, adds the sucrose of 1.25 g and the sulfuric acid of 7.2 mL 0.2 mol/L, ultrasonic 1 h; Under the condition of 90 ℃, moisture is evaporated to constant weight, then at 160 ℃ preliminary carbonization 6 h; The product of preliminary carbonization was ground to 80 mesh sieves, then be dissolved in 11 mL water, again added the sucrose of 0.75 g and the sulfuric acid of 4 mL 0.2 mol/L; Repeat the process of 90 ℃ of moisture evaporations and 160 ℃ of preliminary carbonizations; At N
2protection under, put into 900 ℃, tube furnace insulation, 5 h; It is that 5% HF solution stirring, 24 h remove hard mould agents that products therefrom is dissolved in volume fraction; Centrifugal, with distilled water, be washed till neutrality, be put in 60 ℃ of dry mesoporous carbon carriers that obtain in baking oven.By 0.05 g dissolution of sodium hydroxide in 10 mL distilled water; Add 1 g mesoporous carbon carrier, ultrasonic 1 h; Rotary evaporation is removed moisture, obtains alkaline gold/mesoporous carbon catalyst (5 %wt sodium hydroxide).10 g sewer oils, 0.5 g alkalescence gold/mesoporous carbon catalyst (5 %wt sodium hydroxide) are added to cracking tube.Be warming up to 350 ℃, occur that condensed fluid is to generating without cut.Cracking obtains liquid 6.9 g, carbon residue 2.4 g, non-condensable gases 0.7 g.
embodiment 8:
The mesoporous molecular sieve SBA-15 of 1 g (hard mould agent) is dissolved in the distilled water of 11 mL, adds the sucrose of 1.25 g and the sulfuric acid of 7.2 mL 0.2 mol/L, ultrasonic 1 h; Under the condition of 90 ℃, moisture is evaporated to constant weight, then at 160 ℃ preliminary carbonization 6 h; The product of preliminary carbonization was ground to 80 mesh sieves, then be dissolved in 11 mL water, again added the sucrose of 0.75 g and the sulfuric acid of 4 mL 0.2 mol/L; Repeat the process of 90 ℃ of moisture evaporations and 160 ℃ of preliminary carbonizations; At N
2protection under, put into 900 ℃, tube furnace insulation, 5 h; It is that 5% HF solution stirring, 24 h remove hard mould agents that products therefrom is dissolved in volume fraction; Centrifugal, with distilled water, be washed till neutrality, be put in 60 ℃ of dry mesoporous carbon carriers that obtain in baking oven.By 0.05 g dissolution of sodium hydroxide in 10 mL distilled water; Add 1 g mesoporous carbon carrier, ultrasonic 1 h; Rotary evaporation is removed moisture, obtains alkaline gold/mesoporous carbon catalyst (5 %wt sodium hydroxide).10 g sewer oils, 0.5 g alkalescence gold/mesoporous carbon catalyst (5 %wt sodium hydroxide) are added to cracking tube.Be warming up to 500 ℃, occur that condensed fluid is to generating without cut.Cracking obtains liquid 7.3 g, carbon residue 1.4 g, non-condensable gases 1.3 g.
embodiment 9:
The mesoporous molecular sieve SBA-15 of 1 g (hard mould agent) is dissolved in the distilled water of 11 mL, adds the sucrose of 1.25 g and the sulfuric acid of 7.2 mL 0.2 mol/L, ultrasonic 1 h; Under the condition of 90 ℃, moisture is evaporated to constant weight, then at 160 ℃ preliminary carbonization 6 h; The product of preliminary carbonization was ground to 80 mesh sieves, then be dissolved in 11 mL water, again added the sucrose of 0.75 g and the sulfuric acid of 4 mL 0.2 mol/L; Repeat the process of 90 ℃ of moisture evaporations and 160 ℃ of preliminary carbonizations; At N
2protection under, put into 900 ℃, tube furnace insulation, 5 h; It is that 5% HF solution stirring, 24 h remove hard mould agents that products therefrom is dissolved in volume fraction; Centrifugal, with distilled water, be washed till neutrality, be put in 60 ℃ of dry mesoporous carbon carriers that obtain in baking oven.By 0.05 g dissolution of sodium hydroxide in 10 mL distilled water; Add 1 g mesoporous carbon carrier, ultrasonic 1 h; Rotary evaporation is removed moisture, obtains alkaline gold/mesoporous carbon catalyst (5 %wt sodium hydroxide).10 g sewer oils, 0.1 g alkalescence gold/mesoporous carbon catalyst (5 %wt sodium hydroxide) are added to cracking tube.Be warming up to 420 ℃, occur that condensed fluid is to generating without cut.Cracking obtains liquid 7.8 g, carbon residue 1.4 g, non-condensable gases 0.8 g.
embodiment 10:
The mesoporous molecular sieve SBA-15 of 1 g (hard mould agent) is dissolved in the distilled water of 11 mL, adds the sucrose of 1.25 g and the sulfuric acid of 7.2 mL 0.2 mol/L, ultrasonic 1 h; Under the condition of 90 ℃, moisture is evaporated to constant weight, then at 160 ℃ preliminary carbonization 6 h; The product of preliminary carbonization was ground to 80 mesh sieves, then be dissolved in 11 mL water, again added the sucrose of 0.75 g and the sulfuric acid of 4 mL 0.2 mol/L; Repeat the process of 90 ℃ of moisture evaporations and 160 ℃ of preliminary carbonizations; At N
2protection under, put into 900 ℃, tube furnace insulation, 5 h; It is that 5% HF solution stirring, 24 h remove hard mould agents that products therefrom is dissolved in volume fraction; Centrifugal, with distilled water, be washed till neutrality, be put in 60 ℃ of dry mesoporous carbon carriers that obtain in baking oven.By 0.05 g dissolution of sodium hydroxide in 10 mL distilled water; Add 1 g mesoporous carbon carrier, ultrasonic 1 h; Rotary evaporation is removed moisture, obtains alkaline gold/mesoporous carbon catalyst (5 %wt sodium hydroxide).10 g sewer oils, 1 g alkalescence gold/mesoporous carbon catalyst (5 %wt sodium hydroxide) are added to cracking tube.Be warming up to 500 ℃, occur that condensed fluid is to generating without cut.Cracking obtains liquid 7.0 g, carbon residue 1.3 g, non-condensable gases 1.7 g.
embodiment 11:
In embodiment 6, gained catalyse pyrolysis oil nature is as table 1:
Table 1 catalyse pyrolysis oil properties and literature value comparison
| Character | Catalytic pyrolysis oil | Literature value a |
| Acid number | 25.3 | 116-207 |
| Density (g/cm 3) | 0.86 | 0.818-0.882 |
| Water content | 0.43 | - |
| Calorific value (kJ/g) | 42.6 | - |
| Viscosity (mm 2/s，30 ℃) | 4.4 | 2.7-3.7 |
| Outward appearance | Dark-brown | - |
A. reference [Daniela G. Limaa, Valerio C.D. Soares a, Eric B. Ribeiro a. Diesel-like fuel obtained by pyrolysis of vegetable oils[J]. J. Anal. Appl. Pyrolysis 2004. 71,987-996]
As shown in Table 1, the properties of cracking hydrocarbon oil product is obviously better than literature value, particularly acid number obvious reduction, illustrates that basic catalyst has obvious effect in the regulation and control of cracked oil product acid number.
Claims (1)
1. the method for a mesoporous alkaline carbon material catalytic pyrolysis oil and fat preparation high-performance fuel oil, it is characterized in that comprising the following steps: the hard mould agent mesoporous molecular sieve SBA-15 of 1 g is dissolved in the distilled water of 11 mL, add the sucrose of 1.25 g and the sulfuric acid of 7.2 mL 0.2 mol/L, ultrasonic 1 h; Under the condition of 90 ℃, moisture is evaporated to constant weight, then at 160 ℃ preliminary carbonization 6 h; The product of preliminary carbonization was ground to 80 mesh sieves, then be dissolved in 11 mL water, again added the sucrose of 0.75 g and the sulfuric acid of 4 mL 0.2 mol/L; Repeat the process of 90 ℃ of moisture evaporations and 160 ℃ of preliminary carbonizations; At N
2protection under, put into 900 ℃, tube furnace insulation, 5 h; It is that 5% HF solution stirring, 24 h remove hard mould agents that products therefrom is dissolved in volume fraction; Centrifugal, with distilled water, be washed till neutrality, be put in 60 ℃ of dry mesoporous carbon carriers that obtain in baking oven; By 0.05 g dissolution of sodium hydroxide in 10 mL distilled water; Add 1 g mesoporous carbon carrier, ultrasonic 1 h; Rotary evaporation is removed moisture, obtains the alkaline gold/mesoporous carbon catalyst containing 5 %wt sodium hydroxide, and 10 g sewer oils, 0.5 g are added to cracking tube containing the alkaline gold/mesoporous carbon catalyst of 5 %wt sodium hydroxide; Be warming up to 420 ℃, occur that condensed fluid is to generating without cut, cracking obtains liquid 7.2 g, carbon residue 1.7 g, non-condensable gases 1.1 g.
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