CN109289871A - A kind of preparation method of the carbon-based solid super-strong acid of biomass with classification duct - Google Patents
A kind of preparation method of the carbon-based solid super-strong acid of biomass with classification duct Download PDFInfo
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- CN109289871A CN109289871A CN201811287995.9A CN201811287995A CN109289871A CN 109289871 A CN109289871 A CN 109289871A CN 201811287995 A CN201811287995 A CN 201811287995A CN 109289871 A CN109289871 A CN 109289871A
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- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
Abstract
The present invention relates to catalysis materials to synthesize field, discloses a kind of preparation method with the carbon-based solid super-strong acid of biomass for being classified duct and its application in esterification, etherificate and hydrolysis.Preparation method includes the following steps: (1) using the biomass carbon of hydrothermal carbonization preparation layer structure as raw material, with water glass solution 180oHydro-thermal process is carried out under C, obtains biomass carbon quantum dot-waterglass mixed sols；(2) it will be cooled to this mixed sols of room temperature with mineral acid acidified, then plus pore creating material is 60oC ageing is gel；(3) this gel is obtained into final catalyst through drying, dehydration and sulfonation.The raw material that the preparation method uses is cheap and easy to get, easy to operate；There is more rich particle to heap hole, be distributed in diplopore for prepared catalyst, and sulfonic acid position is abundant, thermal stability is good, acid stronger than the concentrated sulfuric acid, and acid catalysis is high-efficient, and stability is good.
Description
Technical field
The present invention relates to a kind of preparation methods of carbon-based solid super-strong acid of biomass with classification duct.
Background technique
Acid catalysis is widely used to various organic reactions, and such as rearrangement, hydration, hydrolysis, alkylation, is etherified, is different esterification
The reaction such as structure, polymerization, addition and polycondensation, it has also become one of the key transformation technology of production fuel and industrial important chemical.?
Traditional chemical industry, liquid acid such as hydrofluoric acid, especially sulfuric acid are a kind of most popular catalyst, such as are had more than every year
15000000 tons of sulfuric acid is applied to catalytic field.Although the high catalytic efficiency of liquid acid, liquid acid is difficult to recycle but big
Amount use produces a large amount of reluctant spent acid, to cause serious environmental pollution.Currently, " green " in chemical process
Concept excite chemists study various solid acids such as super acids, Si-Al molecular sieve and macropore sulfuric acid resin come replacement can not return
Receipts liquid acid (Acc. Chem. Res., 2002,35 (9): 686-694., Science 2002,297 (5582):
799-803., Chem. Rev., 2002,102 (10): 3641-3666.).However these solid acids are in cost and acid catalysis
Energy aspect can not still strive unexpectedly with the concentrated sulfuric acid.
Super acids (acid strength is also bigger than 100% sulfuric acid) (Acc. Chem. Res., 1968,1 (7): 202-209.)
There is very strong adsorption capacity to protonation substrate, and stabilize some carbon atoms, be widely used in many important organic anti-
Answer, especially hydro carbons conversion (Appl. Catal. A:Gen., 1996,146 (1): 3-32., Science 1997,
276 (5313): 776-779., Science 1979,206 (4414): 13.).Traditionally, super acids be prepared with it is following
Two ways: 1) by fluorine-containing Br nsted acid (HF, FSO3H、CF3SO3H etc.) and fluorination lewis acid (BF3, SBF5, TAF5 etc.)
Mixing；2) based on metal oxide, it is readily synthesized the liquid superacid as homogeneous catalyst；Use SO4 2-、WO4 2-Or
MoO4 2-Oxo anionic treatments Zr, Ti, Fe, A1 or Sn oxide, synthesizes stratiform super acids (Adv. Catal. in which can be convenient
1990,37:165-211.).Improved Solid Acid Strength Measurement Based is being explored, Takagaki et al. discovery is removed with TbAOH aqueous solution
Stratiform presoma, the HTiNbO that then acid precipitation obtains5Nanometer sheet can be obviously improved acidity (corresponding to 90% sulfuric acid or more
(J. Am. Chem. Soc., 2003,125 (18): 5479-5485.) by force).Yang Qi China et al. discovery, in hollow titanium dioxide
In the nano-space of silicon nanosphere, the acid intensity of sulfonated polystyrene nanoparticle can be by its reversible Morphological Transitions from poly-
Collection (enhancing acidity) is changed into swelling (acidity reduction) state to adjust, mainly by interaction of hydrogen bond between adjacent sulfonic acid group
It is formed and destroys (Nat. Commun., 2014,5:3170.).
Since 2005, solid sulfoacid derived from charcoal is compared with macropore sulfate resin, in certain acid catalyzed reactions
It is cheap, be easy to get and activity is high, therefore, it is a kind of extensive solid acid of application prospect, obtain it is worldwide extensively
Pay close attention to (Nature 2005,438:178., Green Chem., 2006,8 (1): 17-21., J. Am. Chem.
Soc., 2008, 130(38): 12787-12793., Catal. Lett., 2009, 131(1): 242-249.,
Chin. J. Catal., 2009, 30(12): 1203-1208., Bioresource Technol., 2013, 133:
618-621., Chem. Mater., 2006, 18(13): 3039-3045., Catal. Commun., 2008, 9(7):
1579-1582.).But the large-scale application of this catalyst nevertheless suffers from limitation, due to their non-porosity and shakiness
Low exposure (ACS Catal., 2012,2 (7): 1296- of fixed fine and close stepped construction and their sulfonic acid sites
1304.).Some effective methods are developed, such as the high warm carbonization (Carbon 2002,40:1181- of catalytic activation
1191., Carbon 1999, 37: 269-274., J. Colloid Interf. Sci., 1995, 176: 422-
431., Carbon 2003,41:267-275.), hard (J. Am. Chem. Soc., 2001,123 (37): 9208-
9209; J. Am. Chem. Soc., 2006, 128(31): 10026-10027., J. Phys. Chem. B 1999,
103: 7743-7746., J. Am. Chem. Soc., 2000, 122: 10712-10713., J. Mater. Chem.,
2005,15:1217-1231.) or soft (Angew. Chem. Int. Ed., 2005,44:7053., Carbon
2004, 42: 767-770., Angew. Chem. Int. Ed., 2004, 43: 5785-5789., J. Am. Chem.
Soc., 2005,127:13508-13509., Chem. Commun., 2005:2125-2127.) template, it is used to prepare
Stable structure and unordered or orderly porous carbon materials and its sulfonated derivative.In the method reported, catalytic activation charing
It should be most competitive, because it provides a kind of simple and practical forming hole method, be used to prepare stable BC material
High surface area (about 1000 m2·g-1) (Catal. Lett., 2009,131 (1): 242-249.), but the method leads to sulphur
Acid groups content sharp fall.
In conclusion having for development compared with Large ratio surface and stablizing cellular structure, the big biology base solid carbon sulphur of acid strength
Acid is still what height was expected." a kind of diapsid silica-biomass carbon is compound for the previous patent that the present invention applies at us
On the basis of the preparation method of solid sulfoacid " (volt recalescence etc., CN 201710824865.3), disclose a kind of with classification duct
The carbon-based solid super-strong acid of biomass preparation method.
Summary of the invention
The object of the present invention is to provide the carbon-based solid super-strong acids of biomass that a kind of cheap, simple synthesis has classification duct
Method.
Preparation of the present invention has the carbon-based solid super-strong acid method of biomass in classification duct, includes the following steps
(preparation method is shown in patent, volt recalescence etc., a kind of preparation method of diapsid silica-biomass carbon complex solid sulfonic acid
CN 201710824865.3):
(1) in the presence of sodium silicate aqueous solution, by biomass carbon in a high pressure reaction kettle 180o9 h of hydro-thermal process is carried out under C,
The layer structure that biomass carbon is destroyed with this, the black liquor for keeping its evenly dispersed formation stable；
(2) it will be as cold as the black liquor and inorganic acid stirring contact acid chemical conversion glue of room temperature obtained by step (1), pore creating material is then added and adds
Heat is to 60oC is stirred to dry acquisition gel；
(3) it by gel drying obtained by step (2) and mills to obtain powder, gained powder is successively carried out to dehydration and sulfonation.
Acidulant used in the present invention is hydrochloric acid or phosphoric acid.
Pore creating material used in the present invention is sodium chloride, sodium dihydrogen phosphate, boric acid, sodium perborate, sodium fluoborate and borax.
Dehydration temperaturre used is 200-350 in the present inventionoC, dewatering time are 5 h.
Sulfonating agent used is the concentrated sulfuric acid in the present invention, dosage by volume of bamboo carbon by weight dosage 10
Times, reaction temperature 100 oC, time are 3 h.
The invention has the following advantages that (1) it is raw materials used it is cheap and easy to get, synthetic method is simple, easy to operate；(2) of the invention
Used in pore creating material inorganic acid or salt it is inexpensive, have the characteristics that environmentally friendly by simply washing to remove, and can realize back
It receives and recycles；(3) present invention is made by sodium dihydrogen phosphate, phosphoric acid, sodium tetraborate, sodium perborate, boric acid, sodium fluoborate modification
Classification duct biomass carbon base solid super-strong acid sour density is high, stability is good, in Synthesis of Adipic Acid Catalyzed dibutyl ester and
There is high catalytic efficiency, the good feature of stability in cellulose hydrolysis.
Specific embodiment
The following examples are however to be not limited to the specific embodiment listed of the present invention to further explanation of the invention
The embodiment of description.
Embodiment 1: biomass carbon base solid super-strong acid method in classification duct of the present invention, comprising the following steps:
(1) the bamboo carbon for weighing the preparation of hydrothermal carbonization method (is denoted as HTBC, preparation method is shown in patent, volt recalescence etc., a kind of superelevation sulphur
The preparation method CN 201710129798.3 of sour density biomass carbon solid acid), 10.1 times amount water glass solution reaction under high pressures
It is mixed in kettle, 180o9 h of hydro-thermal process is carried out under C, so that the removing of biostromal matter carbon is generated carbon quantum dot and waterglass with this
Mixed sols；
(2) after mixed sols obtained by step (1) being as cold as room temperature, carry out acidification plastic with mixed in hydrochloric acid under stiring, then plus
Enter sodium chloride, dosage is 2 times of BC material utilization amount in mass, is stirred dissolution, this mixture is stirring and heating 60oIt is evaporated under C, obtains solid mixture；
(3) by gel obtained by step (2) in 100oC dries 8 h, mills to obtain powder, by gained powder respectively in nitrogen atmosphere
200 oC、250 oC、300 oC and 350oBe dehydrated 5 h under C, obtain black powder material with a large amount of distillation water washings to filtrate without
Chloride ion, then 100oC is dry, and 8 h obtain the powder body material of removal pore creating material；2 g of this powder body material is finally weighed, is added dense
20 mL of sulfuric acid, in 100o3 h of sulfonation under C, until the sulfonate materials of acquisition are washed with distilled water to filtrate sulfate radical-free,
100 oDry 8 h of C obtain classification duct biomass carbon base solid super-strong acid labeled as NaCl-SLBCSA (X, Y), and wherein X is chlorine
Change the dosage of sodium (pore creating material), Y is dehydration temperaturre (corresponding embodiment 1-1 ~ 1-4)；Shown in its result table 1:
Table 1
The NaCl-SLBCSA (2,200 prepared by embodiment 1-1oC), the TMPO absorption in attached drawing 131P-Solid NMR is 90
Ppm strong superpower acid signal more acid than the concentrated sulfuric acid；The sulfonic group content of measurement is 0.9842 mmolg-1；In its attached drawing 2
The sulfonic group thermal decomposition temperature of TGA characterization is 315oC, (preparation method is shown in patent to carbon sulfonic acid more common than reference substance, lies prostrate recalescence
Deng a kind of preparation method CN 201710129798.3 of superelevation sulfonic acid density biomass carbon solid acid is denoted as HTBCS) it is high about
57 oC, duct characterization are detailed in our patent (volt recalescence etc., a kind of diapsid silica-biomass carbon complex solid sulphur
The preparation method CN201710824865.3 of acid).
Embodiment 2: preparation of the present invention is classified duct biomass carbon base solid super-strong acid method, including following step
It is rapid: to be carried out according to the method for embodiment 1-1, the difference is that hydrochloric acid is replaced with phosphoric acid in step (2) and dehydration temperaturre is
250 oC is denoted as H3PO4- SLBCSA (2,250) (for embodiment 2), the results are shown in Table 2.
Embodiment 3: preparation of the present invention is classified duct biomass carbon base solid super-strong acid method, including following step
It is rapid: to be carried out according to the method for embodiment 1-1, the difference is that sodium chloride uses sodium dihydrogen phosphate, high boron respectively in step (2)
Sour sodium, boric acid, sodium fluoborate, borax replace and the dehydration temperaturre in step (3) is 250oC；It is respectively labeled as NaH2PO4-
SLBCSA (2,250), NaBO3- SLBCSA (2,250), HBO3- SLBCSA (2,250), NaBF4- SLBCSA (2,250) and
Na2B4O7- SLBCSA (2,250) (corresponds to embodiment 3-1 ~ 3-5)；NaH2PO4- SLBCSA (2,250oC cryogenic nitrogen aspiration) is used
Desorption characterization, characterization result is that low temperature nitrogen adsorption desorption curve and pore distribution are as shown in Fig. 3, illustrates biphosphate
Influence very little when sodium replaces sodium chloride to pore-forming；The results are shown in Table 2 for it:
Table 2
It as known from Table 2, is 250 in dehydration temperaturreoUnder C, acidulant is changed to phosphoric acid or pore creating material sodium chloride is changed to phosphoric acid
When sodium dihydrogen, sodium perborate, boric acid and sodium fluoborate, prepared classification duct biomass carbon base solid super strong acidic group solid is super
The sulfonic group content of strong acid obviously increases；But pore creating material be borax when, sulfonic group content slightly declines.
Embodiment 4: preparation of the present invention is classified duct biomass carbon base solid super-strong acid method, including following step
It is rapid: to be carried out according to the method for embodiment 3-1, the difference is that the dosage of sodium dihydrogen phosphate is respectively 1 times, 3 times and 4 times and takes off
Coolant-temperature gage is respectively 200oC、300 oC and 350oC(respectively corresponds embodiment 4-1 ~ 4-6), the results are shown in Table 3:
Table 3
As known from Table 3, as the dosage of sodium dihydrogen phosphate is from when increasing to 2 times for 1 times, prepared classification duct biomass carbon base
The sulfonic group content of solid super-strong acid is from 0.7499 mmolg-1Increase to 1.2633 mmolg-1, while sulfonic heat
Stability is also improving；But the dosage of sodium dihydrogen phosphate is further increased, sulfonic group content declines instead and its thermostabilization
Property is also declined；With the raising of dehydration temperaturre, sulfonic group content is decline, this is because the raising of dehydration temperaturre promotes
The further isomery crosslinking of carbon material leads to the reduction in sulfonation site；But the thermal stability of p-sulfonic acid base declines after improving before this.
Embodiment 5: preparation of the present invention is classified duct biomass carbon base solid super-strong acid method, including following step
It is rapid: to be carried out according to the method for embodiment 3-3, the difference is that the dosage of boric acid is respectively 1 times, 3 times and 4 times and dehydration temperaturre
Respectively 200oC、300 oC and 350oC(respectively corresponds embodiment 5-1 ~ 5-6), the results are shown in Table 4:
Table 4
As known from Table 4, as the dosage of boric acid is from when increasing to 2 times for 1 times, prepared classification duct biomass carbon base solid is super
The sulfonic group content of strong acid is from 0.7428 mmolg-1Increase to 1.0018 mmolg-1；But further increase the use of boric acid
Amount, sulfonic group content declines instead, but the thermal stability of p-sulfonic acid base does not have a great impact；With dehydration temperaturre
It improves, sulfonic group content has just begun with promotion (200 ~ 300 slightlyoC), then have in raising dehydration temperaturre sulfonic group content
Slightly decline, the thermal stability of p-sulfonic acid base does not influence significantly.
Embodiment 6: preparation of the present invention is classified duct biomass carbon base solid super-strong acid method, including following step
It is rapid: to be carried out according to the method for embodiment 3-2, the difference is that dehydration temperaturre is respectively 200oC、300 oC and 350oC(difference
Corresponding embodiment 6-1 ~ 6-3), the results are shown in Table 5:
Table 5
As known from Table 5, when using sodium perborate as pore creating material, with the raising of dehydration temperaturre, sulfonic group content is almost without change
Change；But the thermal stability of p-sulfonic acid base is in raising.
Embodiment 7: preparation of the present invention is classified duct biomass carbon base solid super-strong acid method, including following step
It is rapid: to be carried out according to the method for embodiment 3-5, the difference is that dehydration temperaturre is respectively 200oC, 300oC and 350oC(difference
Corresponding embodiment 7-1 ~ 7-3), the results are shown in Table 6:
Table 6
| Embodiment | Catalyst | -SO3H/mmol·g-1 | TSulfonic group decomposition temperature/oC |
| 7-1 | Na2B4O7- SLBCSA (2,200) | 0.5134 | 283 |
| 3-5 | Na2B4O7- SLBCSA (2,250) | 0.5695 | 290 |
| 7-2 | Na2B4O7- SLBCSA (2,300) | 0.8852 | 288 |
| 7-3 | Na2B4O7- SLBCSA (2,350) | 0.6983 | 262 |
As known from Table 6, when using borax as pore creating material, with the raising of dehydration temperaturre, sulfonic group content has just been begun with slightly
It is promoted (200 ~ 300), then has in raising dehydration temperaturre sulfonic group content and slightly decline；But the thermal stability of p-sulfonic acid base is first
It is to decline after improving.
Embodiment 8: preparation of the present invention is classified duct biomass carbon base solid super-strong acid method, including following step
It is rapid: to be carried out according to the method for embodiment 3-4, the difference is that the dosage of sodium fluoborate is respectively 1 times, 3 times and 4 times (right respectively
Answer embodiment 8-1 ~ 8-3), the results are shown in Table 7；
Table 7
| Embodiment | Catalyst | -SO3H/mmol·g-1 | TSulfonic group decomposition temperature/oC |
| 8-1 | NaBF4- SLBCSA (1,250) | 0.7865 | 253 |
| 3-4 | NaBF4- SLBCSA (2,250) | 1.0159 | 254 |
| 8-2 | NaBF4- SLBCSA (3,250) | 0.7567 | 289 |
| 8-3 | NaBF4- SLBCSA (4,250) | 0.6167 | 291 |
As known from Table 7, as the dosage of sodium fluoborate is from when increasing to 2 times for 1 times, prepared classification duct biomass carbon base is solid
The sulfonic group content of body super acids is from 0.7865 mmolg-1Increase to 1.0159 mmolg-1；But further increase fluorine boron
The dosage of sour sodium, sulfonic group content decline instead；But the thermal stability of p-sulfonic acid base is to improve.
Embodiment 9: using material prepared by embodiment 3-1 as catalyst, catalysis isooctanol is reacted with adipic acid synthesizes oneself
Adipate (DOA)；(Zou Yanhong is solid for the research of the specific embodiment reference Zou Yanhong of the method catalyzed and synthesized et al.
Research [D] the Hunan Normal University master thesis of body acid catalysis synthesizing adipic acid dioctyl ester, 2012), wherein specific reaction
Condition includes: 0.3 mol adipic acid, 0.75 mol isooctanol, 1.0 g of catalyst of the invention, and 125oIt is anti-under C reflux state
Answer 2 h.After reaction, catalyst filtration, respectively wash 2 times with water and ethyl alcohol, 110oC is dry to constant weight, and weighing calculates catalysis
The rate of recovery of agent.Ester layer is with 50oC hot water washs 5 times, and catalyst detergent liquid merges with ester layer cleaning solution, uses sodium hydroxide solution
The adipic acid of (0.01 mol/L) titration remaining, calculates esterification yield with this.Using identical reaction temperature, time and acid alcohol ratio,
According to the actual amount of each catalyst, by catalyst: adipic acid: isooctanol=1 g:0.3 mol:0.75 mol input amount is urged
Agent is reused 4 times, shown in result table 8:
Table 8
As known from Table 8, after four secondary responses, esterification yield is basically stable at 99%, shows NaH2PO4- SLBCSA's (2,250)
Catalytic performance is more stable；And its rate of recovery is also stabilized in 98% and also indicates that the structure of the catalyst is more stable.
Embodiment 12: it respectively using material prepared by embodiment 1-2,2,3-1,3-2,3-3,3-4,3-5 as catalyst, urges
The reaction condition of cellulose hydrolysis are as follows: the pretreated microcrystalline cellulose of the phosphoric acid of 2 parts by weight, the dosage of the catalyst are 1
Parts by weight, microwave irradiation power are 400 W, reaction temperature 90-92oC, reaction time are 30 minutes；Hydrolysising product analysis is adopted
With the document (design and imitative enzymatic wood fibre hydrolysis [D] of super ion liquid functionalization biomass carbon sulfonic acid catalyst
Hunan Normal University, 2015.) method of report, (respectively corresponds embodiment 12-1 ~ 12-7) shown in result table 9；
Table 9
As known from Table 9, compared to NaCl-SLBCSA (2,250) by introducing NaH2PO4、H3PO4、NaBO3、HBO3、NaBF4、
Na2B4O7The modified hydrolysis for being conducive to cellulose.
Embodiment 13: respectively with embodiment 1-2,2,3-1,3-2,3-3,3-4,3-5 and common carbon sulfonic acid (HTBCS) and
Common macropore sulfuric acid resin is catalyst, and catalysis methanol reacts synthesizing methyl tertbutyl ether (MTBE) with isobutene (IB)；It is anti-
Answer condition are as follows: 10 g isobutenes, 0.4 g catalyst, 8.6 g methanol, 1.5 MPa of pressure, reaction temperature 65oC, when reaction
Between be 2 h；Pass through the conversion ratio of gas chromatographic analysis IB, (corresponding embodiment that the results are shown in Table 10 using cyclopentanone as internal standard
13-1 ~ 13-9)；
Table 10
As known from Table 10 in catalyzing and synthesizing MTBE performance, the catalytic performance after phosphorous boron compound is compound modified has
It is apparent to improve.
The present invention provides simple, green preparation classification duct biomass carbon base solid super-strong acid a methods.
Detailed description of the invention: Fig. 1 is NaCl-SLBCSA (2,200) and HTBCS31P solid state nmr spectrogram；Fig. 2 is NaCl-
The DTG of SLBCSA (2,200) and HTBCS schemes；Fig. 3 is NaH2PO4The low temperature nitrogen adsorption desorption curve of-SLBCSA (2,250) and
Graph of pore diameter distribution.
Claims (8)
1. a kind of preparation method of the carbon-based solid super-strong acid of biomass with classification duct, which is characterized in that the method packet
Include following steps:
(1) for the biomass carbon (HTBC) for obtaining layer structure with hydrothermal carbonization for raw material, the water glass solution measured with 10.1 times is mixed
It closes, then in a high pressure reaction kettle 180oIt is carried out hydro-thermal process 9 hours under C, so that the removing of biostromal matter carbon is generated carbon amounts with this
Son point and waterglass mixed sols；
(2) it after mixed sols obtained by step (1) being as cold as room temperature, is mixed with inorganic acid carry out acidification plastic under stiring, then
Various pore creating materials are added and are stirred dissolution, this mixture is stirring and heating 60oIt is evaporated under C, obtains solid mixture；
(3) by step (2) obtained solid mixture in 100-120oC dries 12-24 h, then mills as powder, by gained powder
Material is first lower under nitrogen atmosphere, certain temperature to be dehydrated 5 h, then with the concentrated sulfuric acid in 100-120oIt is carried out sulfonation 3-5 hours under C
Obtain final catalyst.
2. according to the method described in claim 1, it is characterized in that inorganic acid used in step (2) is hydrochloric acid, phosphoric acid, concentration
For 6 M, dosage is 15 mL/g BC.
3. according to the method described in claim 1, it is characterized in that pore creating material used in step (2) be sodium chloride, sodium dihydrogen phosphate,
Boric acid, sodium perborate, sodium fluoborate and borax, dosage are 1-4 times of BC material utilization amount in mass.
4. according to the method described in claim 1, it is characterized in that step (3) described dehydration temperaturre is 200 ~ 350oC。
5. hole channel type biomass carbon base solid super-strong acid is prepared in method described in any one of -4 according to claim 1.
6. a kind of method of catalytic esterification synthesizing adipic acid dibutyl ester, this method include under the effect of the catalyst, adipic acid and
Isooctanol reacts synthesizing adipic acid dibutyl ester, which is characterized in that the catalyst is hole channel type biomass described in claim 5
Carbon-based solid super acids；
Preferably, the adipic acid relative to 100 parts by weight, the dosage of the catalyst are 2-4 parts by weight, the acid and the alcohol
Dosage molar ratio be 1:2-3, reaction temperature 120-130oC, reaction time are 2-4 hours.
7. a kind of method of catalyst etherifying synthesizing methyl tertbutyl ether, this method include under the effect of the catalyst, methanol with it is different
Butylene carries out etherification reaction, which is characterized in that the catalyst is that hole channel type biomass carbon base solid described in claim 5 is super
Strong acid；
Preferably, the isobutene relative to 100 parts by weight, the dosage of the catalyst are 2-4 parts by weight, the isobutene and first
The molar ratio of the dosage of alcohol is 1:2-3, reaction temperature 45-65oC, reaction time are 2-4 hours.
8. a kind of method of catalyzing cellulose hydrolysis, this method includes under the effect of the catalyst, which is characterized in that the catalysis
Agent is hole channel type biomass carbon base solid super-strong acid described in claim 5；
Preferably, relative to the pretreated cellulose of phosphoric acid of 2 parts by weight, the dosage of the catalyst is 1 parts by weight, microwave spoke
Penetrating power is 400 W, reaction temperature 90-92oC, reaction time are 30 minutes.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110639554A (en) * | 2019-09-11 | 2020-01-03 | 湖南师范大学 | Method for preparing ultrahigh-thermal-stability carbon-silicon composite solid superacid and reversibly regulating and controlling thermal stability of carbon-silicon composite solid superacid |
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