CN101314138A - Carbonaceous solid acid catalyst prepared by direct sulphonation of biomass - Google Patents
Carbonaceous solid acid catalyst prepared by direct sulphonation of biomass Download PDFInfo
- Publication number
- CN101314138A CN101314138A CNA2008100122198A CN200810012219A CN101314138A CN 101314138 A CN101314138 A CN 101314138A CN A2008100122198 A CNA2008100122198 A CN A2008100122198A CN 200810012219 A CN200810012219 A CN 200810012219A CN 101314138 A CN101314138 A CN 101314138A
- Authority
- CN
- China
- Prior art keywords
- solid acid
- acid catalyst
- carbonaceous solid
- biomass
- biodiesel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 239000011973 solid acid Substances 0.000 title claims abstract description 36
- 239000002028 Biomass Substances 0.000 title claims abstract description 10
- 238000005886 esterification reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003225 biodiesel Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002699 waste material Substances 0.000 claims abstract description 5
- 230000029936 alkylation Effects 0.000 claims abstract description 3
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 3
- 230000032050 esterification Effects 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002023 wood Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 10
- 238000006277 sulfonation reaction Methods 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 8
- -1 polysaccharide compound Chemical class 0.000 claims description 7
- 240000007594 Oryza sativa Species 0.000 claims description 6
- 235000007164 Oryza sativa Nutrition 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 235000009566 rice Nutrition 0.000 claims description 6
- 239000011257 shell material Substances 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 5
- 239000010903 husk Substances 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 239000010902 straw Substances 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 235000000346 sugar Nutrition 0.000 claims description 4
- 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 claims description 3
- 240000007049 Juglans regia Species 0.000 claims description 3
- 235000009496 Juglans regia Nutrition 0.000 claims description 3
- 244000046052 Phaseolus vulgaris Species 0.000 claims description 3
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims description 3
- 244000018633 Prunus armeniaca Species 0.000 claims description 3
- 235000009827 Prunus armeniaca Nutrition 0.000 claims description 3
- 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 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 235000021307 Triticum Nutrition 0.000 claims description 3
- 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 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229920005610 lignin Polymers 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 3
- 239000005017 polysaccharide Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 235000020234 walnut Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 241000218631 Coniferophyta Species 0.000 claims description 2
- 240000006394 Sorghum bicolor Species 0.000 claims description 2
- 235000011684 Sorghum saccharatum Nutrition 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 235000013311 vegetables Nutrition 0.000 claims description 2
- 244000098338 Triticum aestivum Species 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000004519 grease Substances 0.000 abstract description 2
- 238000006053 organic reaction Methods 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 235000021588 free fatty acids Nutrition 0.000 abstract 1
- 230000036571 hydration Effects 0.000 abstract 1
- 238000006703 hydration reaction Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 4
- 229940073769 methyl oleate Drugs 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 235000010980 cellulose Nutrition 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the novel material and novel energy technical field and relates to a method for preparing a carbonaceous solid acid catalyst and biodiesel, in particular to a method for preparing the carbonaceous solid acid catalyst and the biodiesel by directly sulfonating pure natural biomass. The method is characterized in that: pure natural and renewable biomass is used as a raw material, concentrated sulfuric acid is directly used to sulfonate the biomass into biomass-based carbonaceous solid acid catalyst, and a continuous rectification-water separation esterification reaction process is adopted to perform the catalytic esterification reaction between free fatty acid or waste grease and short chain alcohol to produce the biodiesel. The raw material adopted by the method has rich resource and low cost, is purely natural and renewable, and belongs to the waste utilization; the method has simple preparation technology, mild and controllable reaction conditions, and low manufacturing cost; the catalyst has high activity, good stability, easy recovery and no corrosion to equipment, belongs to an environment-friendly catalyst, is suitable for mass industrialized introduction of the biodiesel, and can also be used for organic reactions such as alkylation, hydrolyzation, hydration and so on.
Description
Technical field
The invention belongs to catalyst technical field, relate to a kind of preparation carbonaceous solid acid catalyst and method of bio-diesel oil, particularly a kind of Direct Sulfonation living beings prepare carbonaceous solid acid catalyst and method of bio-diesel oil.
Background technology
Along with petering out of petroleum resources, explore novel energy, imperative.Biodiesel mainly is meant with the animal and plant fat to be that raw material and short chain alcohol are through the synthetic a kind of mixture that contains saturated or bad fatty-acid monoester that obtains of esterification.Because biodiesel has renewable, easily biological-degradable, nontoxic, advantage such as sulfur content is low and the discharge of poisonous waste amount is little, is a kind of regenerative resource of cleaning, belongs to environmentally friendly fuel, is the good substitute of conventional oil diesel oil.
Chemical method production biodiesel mainly is to adopt the two-step method of chemical catalysis such as acid system, alkaline process and the two combination.Acid catalyzed process can solve the problem that high acid value or water-containing material are difficult to utilize, the catalyst that adopts mainly is the homogeneous catalyst such as the concentrated sulfuric acid at present, phosphoric acid, hydrochloric acid and various organic sulfonic acid, therefore, exist complex technical process, equipment anticorrosion requires high, and catalyst recovery utilization, the refining difficulty of by-product glycerin, follow-up washing and neutralization produce problems such as waste water.And the use of solid acid catalyst is for addressing the above problem thinking and the direction that provides new.
Carbonaceous solid acid catalyst is a kind of novel solid acid catalyst, the earliest (Nature, Vol.438,10Nov., 2005) that proposed by Japanese scholar.They are raw material with sugar, starch or cellulose, adopt first charing after Sulfonated method prepare carbonaceous solid acid catalyst.This catalyst is used to prepare its catalytic activity of biodiesel apparently higher than other solid acid catalysts, and cheap, the recycling good stability.The quick China of ancestor is raw material with the saccharide compound at home, adopts identical process route also to prepare the carbonaceous solid acid catalyst (publication number: CN1899691A) with high catalytic activity.Yet along with the quick rise of raw material resources prices such as sugar, starch or cellulose in recent years, the price advantage of prepared carbonaceous catalyst disappears.In order to address this problem, we have proposed with pure natural, cheap living beings is raw material, and according to its The Nomenclature Composition and Structure of Complexes characteristics, the biocarbon solid acid catalyst that adopts the technology path of first low-temperature carbonization, rear oxidation, sulfonation again and method to prepare low cost, high activity, can reuse.Propose employing continuous rectification-minute water esterification reaction tech production method of bio-diesel oil, shortened reaction time of esterification, improved esterification efficient (application number: 200810012062.9).
Summary of the invention
The technical problem to be solved in the present invention provides a kind of carbonaceous solid acid catalyst of Direct Sulfonation living beings preparation, so that simplify the preparation technology of carbonaceous solid acid catalyst, reduces production costs.
The present invention prepares biocarbon solid acid catalyst with concentrated sulfuric acid Direct Sulfonation living beings, and its technical scheme comprises the steps:
(1) natural biomass of Xuan Zeing is: wood chip, branch, cellulose, lignin, rice husk, shell, straw a kind of, and it is crushed to granularity is 0.3～10mm; Perhaps be a kind of of polysaccharide compounds such as sugar, starch.
(2) above-mentioned living beings are directly added carrying out sulfonating reaction in the concentrated sulfuric acid (concentration 9Swt%) under nitrogen protection, is to stir 0.5～5h under 25～100 ℃ the condition to obtain reactant mixture at sulfonation temperature; Reactant mixture that will obtain adds and stirs in the distilled water fully, filters, dry, washing, drying can obtain biocarbon solid acid catalyst once more; The consumption mass ratio of the described sample and the concentrated sulfuric acid is 1: 6～20.
(3) esterification that adopts continuous rectification-minute water esterification reaction tech to carry out FFA or waste oil and short chain alcohol prepares biodiesel; Described esterification reaction temperature is 70～100 ℃, and reaction time of esterification is: 1～7h, and molar ratio of methanol to oil is: 4～10: 1, the catalyst amount mass percent is: 4～10%.
Described wood chip is a kind of of conifer wood chip or broad-leaved class wood chip or mixture or pure wood chip of free from admixture of single seeds or the pure wood chip mixture of free from admixture of multiple seeds that it is multiple;
Described shell is a kind of of walnut shell, apricot shell, coconut husk or mixture that it is multiple;
Described stalk is a kind of of wheat straw, beans bar, cornstalk, rice bar, sorghum rod, vegetable seed beam hanger or mixture that it is multiple;
Described saccharide compound is a kind of of glucose, sucrose or mixture that it is multiple;
Effect of the present invention and benefit are:
It is the feedstock production carbonaceous solid acid catalyst that the present invention adopts pure-natural biological matter, and therefore, it is renewable, cheap that raw material resources are enriched;
The inventive method catalyst preparation process process is simple, and the reaction condition gentleness is controlled, and production cost is low;
The solid acid catalyst of the inventive method preparation, active high, good stability, recovery is reused effective; Be used for the reaction of catalysis fatty acids grease and short chain alcohol, can simplify the preprocessing process of glyceride stock, increase the output of biodiesel, environmental protection is suitable for large-scale industrial production.And can also be used for many organic reactions such as alkylation, hydrolysis, aquation;
Continuous rectification of the present invention-minute water esterification reaction tech, the reaction condition gentleness is controlled, simplifies the preparation technology of biodiesel, shortens reaction time of esterification, has improved esterification efficient.
The specific embodiment
Be described in detail the specific embodiment of the present invention below in conjunction with technical scheme.
Embodiment one
The wood chip, wheat straw, beans bar, cornstalk, rice bar, lignin, rice husk, walnut shell, apricot shell, glucose, sucrose, the starch that take by weighing the 14g drying directly add concentrated sulfuric acid 140g respectively; logical people's nitrogen protection; under 25 ℃ of conditions of normal temperature, carry out sulfonating reaction; stir speed (S.S.) remains on about 600r/min; after the reaction 4h; reactant mixture is joined fully stirring in the 300ml distilled water; filter then, drying; wash repeatedly with 100 ℃ of distilled water again; be neutral fully up to filtrate, drying can obtain carbonaceous solid acid catalyst.
Catalytic effect: pack in continuous rectification-minute water esterification device 14g methyl alcohol, 15.86g oleic acid and 1g carbonaceous catalyst carry out esterification (reboiler temperature is 85 ℃) at 90 ℃, react obtain methyl oleate output after 2 hours and conversion rate of esterification as shown in table 1.
The catalytic esterification effect of the solid acid catalyst of table 1, the preparation of different biomass material
Embodiment two
The wood chip that takes by weighing the 14g drying directly adds concentrated sulfuric acid 98g; logical people's nitrogen protection; under 100 ℃ of conditions, carry out sulfonating reaction; stir speed (S.S.) remains on about 600r/min, after the reaction 1h, reactant mixture is joined fully stirring in the 300ml distilled water; filter then, drying; wash repeatedly with 100 ℃ of distilled water, be neutral fully up to filtrate, drying can obtain carbonaceous solid acid catalyst.
Catalytic effect: catalytic effect: pack in continuous rectification-minute water esterification device 14g methyl alcohol, 15.86g oleic acid and 1g carbonaceous catalyst carry out esterification (reboiler temperature is 85 ℃) at 70 ℃, react and obtain methyl oleate 15.39g after 6 hours, esterification yield is 97.03%.
Embodiment three
Take by weighing the 14g dried wood chips and directly add concentrated sulfuric acid 140g; logical people's nitrogen protection; under 50 ℃ of conditions, carry out sulfonating reaction; stir speed (S.S.) remains on about 600r/min, after the reaction 3h, reactant mixture is joined fully stirring in the 300ml distilled water; filter then, drying; wash repeatedly with 100 ℃ of distilled water, be neutral fully up to filtrate, drying can obtain carbonaceous solid acid catalyst.
Catalytic effect: catalytic effect: pack in continuous rectification-minute water esterification device 14g methyl alcohol, 15.86g oleic acid and 0.8g carbonaceous catalyst carry out esterification (reboiler temperature is 85 ℃) at 100 ℃, react and obtain methyl oleate 15.26g after 1 hour, esterification yield is 96.22%.
Embodiment four
Take by weighing the 14g dried wood chips and directly add concentrated sulfuric acid 140g; logical people's nitrogen protection; under 50 ℃ of conditions, carry out sulfonating reaction; stir speed (S.S.) remains on about 600r/min, after the reaction 3h, reactant mixture is joined fully stirring in the 300ml distilled water; filter then, drying; wash repeatedly with 100 ℃ of distilled water, be neutral fully up to filtrate, drying can obtain carbonaceous solid acid catalyst.
Catalytic effect: catalytic effect: pack in continuous rectification-minute water esterification device 14g methyl alcohol, 15.86g oleic acid and 1.5g carbonaceous catalyst carry out esterification (reboiler temperature is 85 ℃) at 80 ℃, react and obtain methyl oleate 15.56g after 1 hour, esterification yield is 98.12%.
Claims (8)
1. the carbonaceous solid acid catalyst of Direct Sulfonation living beings preparation is to be the method for feedstock production carbonaceous solid acid catalyst with pure natural, reproducible living beings, it is characterized in that:
(1) natural biomass of Xuan Zeing is: wood chip, branch, cellulose, lignin, rice husk, shell, straw or polysaccharide compound a kind of; For natural biomass it being crushed to granularity is that 0.3～10mm uses;
(2) above-mentioned natural biomass directly being added in the concentrated sulfuric acid of mass percent 98% carry out sulfonating reaction under nitrogen protection, is to stir 0.5～5h under 25～100 ℃ the condition to obtain reactant mixture at sulfonation temperature; Reactant mixture that will obtain adds and stirs in the distilled water fully, filters, dry, washing, drying obtains biocarbon solid acid catalyst again; The consumption mass ratio of the described sample and the concentrated sulfuric acid is 1: 6～20.
2. utilize the described carbonaceous solid acid catalyst of claim 1 to prepare biodiesel, it is characterized in that the esterification of carrying out FFA or waste oil and short chain alcohol in continuous rectification-minute water esterification device prepares biodiesel; Described esterification reaction temperature is 70～100 ℃, and reaction time of esterification is: 1～7h, and molar ratio of methanol to oil is: 4～10: 1, the catalyst amount mass percent is: 4～10%.
3. carbonaceous solid acid catalyst according to claim 1 is characterized in that: described wood chip is one or more a mixture of conifer wood chip, broad-leaved class wood chip; The perhaps pure wood chip mixture of the free from admixture of pure wood chip of the free from admixture of single seeds or multiple seeds.
4. carbonaceous solid acid catalyst according to claim 1 is characterized in that: described shell is one or more a mixture of walnut shell, apricot shell, coconut husk.
5. carbonaceous solid acid catalyst according to claim 1 is characterized in that: described stalk is one or more a mixture of wheat straw, beans bar, cornstalk, rice bar, sorghum rod, vegetable seed beam hanger.
6. the carbonaceous solid acid catalyst of Direct Sulfonation living beings preparation according to claim 1, it is characterized in that: described polysaccharide compound is sugar or starch; Saccharide compound is one or more a mixture of glucose, sucrose.
7. carbonaceous solid acid catalyst according to claim 1 is characterized in that: stir its speed in the described sulfonating reaction at 300r/min～700r/min.
8. carbonaceous solid acid catalyst according to claim 1 is characterized in that: carbonaceous solid acid catalyst is used for alkylation, hydrolysis or aquation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100122198A CN101314138A (en) | 2008-07-07 | 2008-07-07 | Carbonaceous solid acid catalyst prepared by direct sulphonation of biomass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100122198A CN101314138A (en) | 2008-07-07 | 2008-07-07 | Carbonaceous solid acid catalyst prepared by direct sulphonation of biomass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101314138A true CN101314138A (en) | 2008-12-03 |
Family
ID=40105374
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100122198A Pending CN101314138A (en) | 2008-07-07 | 2008-07-07 | Carbonaceous solid acid catalyst prepared by direct sulphonation of biomass |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101314138A (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101485997B (en) * | 2009-02-12 | 2011-03-30 | 华东理工大学 | Method for preparing carboneous solid acid catalyst |
| CN101659683B (en) * | 2009-08-07 | 2012-02-01 | 厦门大学 | Preparation method of methyl glucoside |
| CN102965202A (en) * | 2012-10-31 | 2013-03-13 | 潍坊金信达生物化工有限公司 | Preparation method of biodiesel by using heterogeneous catalyst |
| CN102965203A (en) * | 2012-10-31 | 2013-03-13 | 潍坊金信达生物化工有限公司 | Method for preparing biodiesel through catalysis of natural biomass solid acid catalyst |
| CN103212440A (en) * | 2013-04-17 | 2013-07-24 | 北京化工大学 | Lignin base solid acid catalyst and preparation process thereof |
| CN103285883A (en) * | 2013-06-28 | 2013-09-11 | 黑龙江大学 | Preparation method of carbon-based sulfoacid solid acid catalyst |
| CN103614244A (en) * | 2013-12-02 | 2014-03-05 | 江南大学 | Method for preparing biodiesel by using carbon-based sulfonic acid functionalized solid acid as catalyst |
| CN104525200A (en) * | 2014-12-04 | 2015-04-22 | 江南大学 | Catalyst for obtaining 5-hydroxymethylfurfural (HMF) by catalytic degradation of biomass resources |
| CN105013538A (en) * | 2014-12-01 | 2015-11-04 | 青岛科技大学 | Preparation method for hydrophobically modified magnetic carbonaceous solid acid catalyst and application of catalyst |
| CN106179404A (en) * | 2016-07-12 | 2016-12-07 | 江苏大学 | A kind of biomass carbon based solid acid for 5 Hydroxymethylfurfural synthesis and preparation method thereof |
| WO2016192175A1 (en) * | 2015-05-29 | 2016-12-08 | 广州澳银生物科技有限公司 | Method for preparing solid acid catalyst with high acid content |
| CN109046381A (en) * | 2018-06-02 | 2018-12-21 | 太原理工大学 | A kind of sulphur carbon-based solid acid catalyst |
| US10227666B2 (en) | 2015-12-10 | 2019-03-12 | Industrial Technology Research Institute | Solid catalysts and method for preparing sugars using the same |
| CN110227547A (en) * | 2019-05-28 | 2019-09-13 | 济南大学 | A kind of preparation method and applications of sulfomethylated lignin acid catalyst |
| CN113617332A (en) * | 2021-08-27 | 2021-11-09 | 郑子渝洋 | Sulfonated biochar for treating heavy metal waste liquid |
| CN113856662A (en) * | 2021-11-01 | 2021-12-31 | 贵州大学 | Layered charcoal catalyst and application thereof in preparation of biodiesel by catalyzing grease |
| CN114192186A (en) * | 2020-09-02 | 2022-03-18 | 中国人民大学 | Carbon-based catalyst material and preparation method and application thereof |
| US11414623B2 (en) | 2019-05-29 | 2022-08-16 | King Fahd University Of Petroleum And Minerals | Efficient biomass carbon-based solid acid esterification catalyst for producing biodiesel |
-
2008
- 2008-07-07 CN CNA2008100122198A patent/CN101314138A/en active Pending
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101485997B (en) * | 2009-02-12 | 2011-03-30 | 华东理工大学 | Method for preparing carboneous solid acid catalyst |
| CN101659683B (en) * | 2009-08-07 | 2012-02-01 | 厦门大学 | Preparation method of methyl glucoside |
| CN102965202B (en) * | 2012-10-31 | 2014-02-19 | 潍坊金信达生物化工有限公司 | Preparation method of biodiesel by using heterogeneous catalyst |
| CN102965203A (en) * | 2012-10-31 | 2013-03-13 | 潍坊金信达生物化工有限公司 | Method for preparing biodiesel through catalysis of natural biomass solid acid catalyst |
| CN102965203B (en) * | 2012-10-31 | 2014-06-25 | 潍坊金信达生物化工有限公司 | Method for preparing biodiesel through catalysis of natural biomass solid acid catalyst |
| CN102965202A (en) * | 2012-10-31 | 2013-03-13 | 潍坊金信达生物化工有限公司 | Preparation method of biodiesel by using heterogeneous catalyst |
| CN103212440A (en) * | 2013-04-17 | 2013-07-24 | 北京化工大学 | Lignin base solid acid catalyst and preparation process thereof |
| CN103212440B (en) * | 2013-04-17 | 2016-01-13 | 北京化工大学 | A kind of lignin base solid acid catalyst and preparation technology thereof |
| CN103285883A (en) * | 2013-06-28 | 2013-09-11 | 黑龙江大学 | Preparation method of carbon-based sulfoacid solid acid catalyst |
| CN103614244A (en) * | 2013-12-02 | 2014-03-05 | 江南大学 | Method for preparing biodiesel by using carbon-based sulfonic acid functionalized solid acid as catalyst |
| CN105013538B (en) * | 2014-12-01 | 2019-04-09 | 青岛科技大学 | A kind of preparation method and applications of the magnetic carbonaceous solid acid catalyst of hydrophobically modified |
| CN105013538A (en) * | 2014-12-01 | 2015-11-04 | 青岛科技大学 | Preparation method for hydrophobically modified magnetic carbonaceous solid acid catalyst and application of catalyst |
| CN104525200A (en) * | 2014-12-04 | 2015-04-22 | 江南大学 | Catalyst for obtaining 5-hydroxymethylfurfural (HMF) by catalytic degradation of biomass resources |
| WO2016192175A1 (en) * | 2015-05-29 | 2016-12-08 | 广州澳银生物科技有限公司 | Method for preparing solid acid catalyst with high acid content |
| US10883151B2 (en) | 2015-12-10 | 2021-01-05 | Industrial Technology Research Institute | Solid catalysts |
| US10227666B2 (en) | 2015-12-10 | 2019-03-12 | Industrial Technology Research Institute | Solid catalysts and method for preparing sugars using the same |
| CN106179404A (en) * | 2016-07-12 | 2016-12-07 | 江苏大学 | A kind of biomass carbon based solid acid for 5 Hydroxymethylfurfural synthesis and preparation method thereof |
| CN109046381A (en) * | 2018-06-02 | 2018-12-21 | 太原理工大学 | A kind of sulphur carbon-based solid acid catalyst |
| CN109046381B (en) * | 2018-06-02 | 2021-06-01 | 太原理工大学 | Sulfur-carbon based solid acid catalyst |
| CN110227547A (en) * | 2019-05-28 | 2019-09-13 | 济南大学 | A kind of preparation method and applications of sulfomethylated lignin acid catalyst |
| US11414623B2 (en) | 2019-05-29 | 2022-08-16 | King Fahd University Of Petroleum And Minerals | Efficient biomass carbon-based solid acid esterification catalyst for producing biodiesel |
| CN114192186A (en) * | 2020-09-02 | 2022-03-18 | 中国人民大学 | Carbon-based catalyst material and preparation method and application thereof |
| CN113617332A (en) * | 2021-08-27 | 2021-11-09 | 郑子渝洋 | Sulfonated biochar for treating heavy metal waste liquid |
| CN113856662A (en) * | 2021-11-01 | 2021-12-31 | 贵州大学 | Layered charcoal catalyst and application thereof in preparation of biodiesel by catalyzing grease |
| CN113856662B (en) * | 2021-11-01 | 2024-02-20 | 贵州大学 | Layered biochar catalyst and application thereof in preparation of biodiesel by catalyzing grease |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101314138A (en) | Carbonaceous solid acid catalyst prepared by direct sulphonation of biomass | |
| CN101298566A (en) | Method for preparing biocarbon solid acid catalyst and biodiesel | |
| ES2733218T3 (en) | Enzymatic cellulose hydrolysis | |
| CN101372539B (en) | Method for producing environment-friendly type plasticiser using waste oil and oil foot | |
| CN101130793A (en) | Novel method for producing fuel alcohol by rice hull and comprehensive utilization of resource | |
| CN100590177C (en) | Process of preparing biodiesel oil with pricklyash seed oil in high acid value | |
| CN101020864A (en) | Stepped high valent acid vegetable oil catalyzing process for preparing fatty acid methyl ester | |
| CN104311411B (en) | The method of levulinic acid is prepared in multistage acid hydrolysis | |
| CN102766703B (en) | Hydrolysis method for hemicelluloses of lignocelluloses | |
| CN113214196B (en) | Method for preparing bio-based chemicals by using lignocellulose biomass as raw material | |
| Wu et al. | Research progress on the preparation and application of biomass derived methyl levulinate | |
| CN108855135A (en) | A kind of carbon-based solid acid catalyst and its application in lignocellulosic depolymerization | |
| Saikia et al. | Sulphonated cellulose-based carbon as a green heterogeneous catalyst for biodiesel production: process optimization and kinetic studies | |
| CN111423399B (en) | Method for converting holocellulose into furfural platform compound | |
| CN101012388A (en) | Method of manufacturing biological diesel oil from hogwash oil | |
| CN102824928B (en) | Solid acid catalyst for preparing biodiesel and preparation method as well as application of solid acid catalyst | |
| CN101245252B (en) | Method for producing biological diesel oil by using waste oil | |
| CN101328446B (en) | Litsea cubeba nucleolus deep-processing and comprehensive utilization process | |
| CN102921399A (en) | Method for preparing solid catalyst | |
| KR100790298B1 (en) | Manufacturing method of high purity fatty acid alkylester and fatty acid alkylester manufactured therefrom | |
| CN100523131C (en) | Esterification reaction technique of preparing biodiesel by waste oil | |
| CN1923990B (en) | Process for preparing fatty acid ester | |
| CN101497803A (en) | Biodiesel and preparing technology thereof | |
| CN103157509A (en) | Carbon-based solid sulfonic acid preparation method using bagasse | |
| CN100494317C (en) | Production of biological diesel oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20081203 |