CN109265707A - A method of separation wood lignin - Google Patents
A method of separation wood lignin Download PDFInfo
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- CN109265707A CN109265707A CN201811129799.9A CN201811129799A CN109265707A CN 109265707 A CN109265707 A CN 109265707A CN 201811129799 A CN201811129799 A CN 201811129799A CN 109265707 A CN109265707 A CN 109265707A
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- Prior art keywords
- lignin
- acid
- formic acid
- methyl benzenesulfonic
- filter
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- 229920005610 lignin Polymers 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000002023 wood Substances 0.000 title claims abstract description 10
- 238000000926 separation method Methods 0.000 title abstract description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 49
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 235000019253 formic acid Nutrition 0.000 claims abstract description 21
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 241000219000 Populus Species 0.000 claims description 19
- 239000000706 filtrate Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 235000021110 pickles Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 abstract description 11
- 229920002678 cellulose Polymers 0.000 abstract description 10
- 239000001913 cellulose Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 238000004904 shortening Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 21
- FVBOICAOEHSWOH-UHFFFAOYSA-N formic acid;4-methylbenzenesulfonic acid Chemical compound OC=O.CC1=CC=C(S(O)(=O)=O)C=C1 FVBOICAOEHSWOH-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 239000000835 fiber Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 5
- 229910001626 barium chloride Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 210000000630 fibrocyte Anatomy 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- WDFZWSZNOFELJY-OLQVQODUSA-N (1R,6S)-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical group C1=CC=C[C@H]2O[C@H]21 WDFZWSZNOFELJY-OLQVQODUSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 244000297179 Syringa vulgaris Species 0.000 description 1
- 235000004338 Syringa vulgaris Nutrition 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KIDZHLOYQHOMOL-UHFFFAOYSA-N benzenesulfonic acid formic acid Chemical compound C1(=CC=CC=C1)S(=O)(=O)O.C(=O)O KIDZHLOYQHOMOL-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000003250 coal slurry Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- IIEZZHAKHPDYBD-UHFFFAOYSA-N ethoxy-hydroxy-oxoazanium Chemical group CCO[N+](O)=O IIEZZHAKHPDYBD-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compounds Of Unknown Constitution (AREA)
Abstract
The present invention provides a kind of method for separating wood lignin, can isolate lignin under conditions of protecting cellulose not oxidized；Solve the problems, such as that traditional slurrying isolated lignin process cycle is long, energy consumption is high, chemicals recycling is difficult.Compared with prior art, the present invention shortening reaction time, energy consumption is low in separation process, reaction condition is mild, and drug price is cheap and is easy to get, and p-methyl benzenesulfonic acid, formic acid are easily recycled, p-methyl benzenesulfonic acid, the formic acid of recycling can reuse, and save the cost belongs to environmentally friendly.
Description
Technical field
The invention belongs to lignin separation technology fields in timber, and in particular to a kind of p-methyl benzenesulfonic acid-formic acid separation timber
The method of lignin.
Background technique
Lignin as the most abundant organic matter of second (cellulose is first) in the world, be it is a kind of it is easy to use can
Regenerated resources, separation is using as focus concerned by people in recent years.Lignin is that three kinds of benzene oxide units pass through ehter bond and carbon
The boiomacromolecule with tridimensional network that carbon key is interconnected to form plays resistance to compression work between cellulose fibre
With.Its purposes is very extensive, such as in the oil industry, can do heavy crude thinner, high temperature tune flux, grease coagulant etc..Except this
Except can also do cement water reducing agent, urea-formaldehyde adhesive prepares surfactant, soil conditioner, prepares novel water-coal-slurry
Additive etc..Lignin is also applied to rubber industry, is used as rubber reinforcing filler, gum filler etc..
But lignin is studied, first has to isolate lignin.Industrially, lignin products to be obtained mainly it is exactly by by alkali
For black liquid separation obtained in method slurrying and sulfite pulping come what is obtained, the Lignin Molecular Weight obtained under this approach is past
It is arrived between tens of thousands of toward hundreds of, they have the distribution of significant wide molecular weight, so as to cause industrial lignin without stabilization
Thermal transition temperature the characteristics of, the lignin in addition to this obtained by this method is also unfavorable for deeper development and utilization.
And traditional lignin separation method also can cause environmental pollution, and it is extremely urgent to develop new lignin separation method.
It is existing to use acid, alkali, overcritical, two water phases, the method for mitigating the means separating lignins such as hydrogenolysis, ionic liquid.Acid
Lignin includes klason lignin, periodic acid lignin, phosphoric acid lignin etc., and Klason chemical modification of lignin is big, unfavorable
In the utilization of lignin.Periodic acid lignin is aoxidized, and phosphoric acid lignin condition mitigates, and chemical modification is small, but has one
Fixed polymerization.Alkali lignin is conducive to lignin dissolution in heating, and chemical modification occurs for lignin during this.Alkali soluble lignin oxygen
Change serious, carbonyl and carboxyl increase.For organic solvent type lignin other than dioxacyclohexanes, organic solvent is pure in conjunction with lignin
Degree is not high, is not easily recycled.
Summary of the invention
The present invention provides a kind of method for separating wood lignin, can divide under conditions of protecting cellulose not oxidized
Separate out lignin；Solve the problems, such as that traditional slurrying isolated lignin process cycle is long, energy consumption is high, chemicals recycling is difficult.
The method of separation wood lignin of the invention, comprises the following steps that
1) wood powder is added in 60 DEG C -90 DEG C of toluenesulfonic acid-formic acid solution and is reacted；
Toluenesulfonic acid-the formic acid solution, wherein the volume ratio of toluenesulfonic acid and formic acid is 1-20:1；
Preferably, the volume ratio that wherein toluenesulfonic acid and formic acid are is 5:1,
The reaction is that revolving reaction or oscillating reactions are carried out under the conditions of water bath with thermostatic control；
2) after reaction, separating filtrate and filter residue；Filtrate is diluted with deionized water, precipitating is generated, will precipitate
It filters out and obtains lignin and acid pickle；
The spent acid first passes through distillation, recycles formic acid, then pass through cooling concentration and recovery p-methyl benzenesulfonic acid again；
The wood powder, preferably cotton wood powder.
In the step 2), the usage amount of deionized water is the ph value 7.0-7.5 for making filtrate.
Compared with prior art, the beneficial effects of the invention are that:
The present invention handles timber using a kind of novel separation method p-methyl benzenesulfonic acid-formic acid, and then isolates in timber
Various substances.Lignin can be isolated under the premise of protecting cellulose not oxidized.
Compared with prior art, the present invention this method can dissolve greatly in relatively low temperature, in the short time
Measure lignin；And the condition that traditional handicraft reaches same effect needs is harsher.
Compared with prior art, the present invention shortening reaction time, energy consumption is low in separation process, and reaction condition is mild,
Drug price is cheap and is easy to get, and p-methyl benzenesulfonic acid, formic acid are easily recycled, and p-methyl benzenesulfonic acid, the formic acid of recycling can reuse,
Save the cost belongs to environmentally friendly.
The method and process simple possible and safety of isolated lignin of the present invention, convenient for operation.
It is the method and process route economy of isolated lignin of the present invention, environmentally protective, it is easy to realization of industrialization.
Detailed description of the invention
Fig. 1: the infrared analysis figure of the lignin extracted in the filtrate of embodiment 4.
Fig. 2: the filter residue in the product and embodiment 4 in embodiment 2 carries out X-ray diffraction (XRD) analysis chart.
Fig. 3: the sem analysis figure of poplar sawdust, fiber in embodiment 1 and embodiment 4.
Specific embodiment
The present invention separates the lignin in poplar, p-methyl benzenesulfonic acid-formic acid isolated lignin using p-methyl benzenesulfonic acid-formic acid
A large amount of lignin can be isolated in the short time, and right at low temperature (traditional subtraction slurrying isolated lignin needs 140-160 DEG C)
Toluenesulfonic acid and formic acid recovery process are extremely convenient, and lignin can be isolated under conditions of protecting cellulose not oxidized by reaching.
The affected step of the present invention is described in detail combined with specific embodiments below, but not as the limitation of the invention.
Embodiment 1: survey poplar in lignin content the following steps are included:
(a) ethyl alcohol and 113.33 milliliters of benzene for measuring 56.67 milliliter 72% are uniformly mixed, and have configured benzene-alcohol mixeding liquid
It is spare.1.0023g poplar sawdust accurately is weighed, is wrapped with qualitative filter paper, is tied with line.It puts in people's Soxhlet extractor with benzene -ol
Mixed liquor extracts six hours in boiling water, then takes out sample and air-dries.
(b) filter paper packet is unlocked, air-dried sample is carefully moved into people 250ml in the conical flask of ground glass stopper, adds people
15ml is pre-adjusted 72% sulfuric acid that temperature is 13 DEG C, sways 1min, impregnates sample by acid completely, then places it in
Kept for two hours sway always in insulating process in 18 DEG C of water bath and at this temperature.
(c) after two hours, sample distillation is washed in one liter of conical flask, and the concentration of dilute acid is 3%, it is added
Distilled water adds up to 560ml including flushing water.Reflux condenser is loaded on conical flask, boils 4h.
(d) heating finishes, and stands, insoluble matter is made to precipitate, the 1G3 then crossed with preparatory constant weight, mistake in glass filter
Filter, reusable heat distills water washing residue, until washing lotion is no acidic, with the not aobvious muddiness of 10% barium chloride solution examination.It inhales
Dry filtrate, takes out filter, and cleaned outside filter with distilled water, and filter and residue are placed in baking oven, are dried to perseverance at 105 DEG C
Weight, obtains lignin.
Lignin content is 28.12% in poplar sawdust used in the present invention.
Embodiment 2: measurement poplar in content of cellulose the following steps are included:
(a) take 800ml chemistry straight alcohol (95%) in the 1000ml beaker of a clean dried with clean dried graduated cylinder, then
It takes the pure nitric acid (relative density 1.42) of 200ml chemistry to be poured into ethyl alcohol by several times slowly with another clean dried graduated cylinder, is added every time
About 10ml, and continuously added after being stirred evenly with glass bar.
(b) 1.0134g poplar sawdust accurately is weighed in the conical flask of 250ml clean dried, 25ml nitric acid ethyl alcohol is added
Mixed solution loads onto reflux condenser, until heating 1h on boiling water bath, during heating, should sway conical flask at any time.
(c) condenser pipe is removed, conical flask is removed from water-bath, a moment is stood, uses gradient method after residue deposition
The 1G of constant weight2.It is filtered in glass filter, flows out residue as far as possible.
(d) filtrate in filter is blotted with vacuum pump, then moves people's conical flask for the residue in filter is flowed into glass bar
In.
(e) 25m nitric acid alcohol mixed solution is measured, the residue of filter and dimension shape bottleneck attachment is moved into conical flask, dress
Upper condensation reflux device, then 1h is heated on boiling water bath.During heating.It should be noted that conical flask is swayed frequently,
(f) it is so repeated 3 times, until fiber bleaches.
(g) conical flask content is all finally moved into filter, washs residue with 10mI nitric acid alcohol mixed solution, then use
Hot water washs until washing lotion methyl orange reagent is not in acidity.Finally twice with ethanol washing.
(h) washing lotion is blotted, filter is taken out, will be cleaned, moved in people's baking oven outside filter with distilled water, dried in (105 scholar 3) DEG C
Drying to constant weight in case.
(i) weighing and calculating content of cellulose.
Content of cellulose is 58.3% in poplar sawdust used in the present invention.
Embodiment 3: the present embodiment isolated lignin method the following steps are included:
(a) according to p-methyl benzenesulfonic acid: formic acid volume ratio is the condition of 1:1, takes 37.5102 grams of p-methyl benzenesulfonic acid, quality dense
Degree weighs 42.6023 grams for 88% formic acid, measures 50ml deionized water in the flask of 500ml, configures 60% mass concentration
P-methyl benzenesulfonic acid-formic acid solution, p-methyl benzenesulfonic acid-formic acid solution is heated.
(b) 60 DEG C are heated to p-methyl benzenesulfonic acid-formic acid solution, 5 grams of poplar sawdusts, the size of poplar sawdust is then added
For 30~50 mesh, flask is put into 100rpm thermostatic control oscillator vibration, 5 minute reaction time was set, starts to react.
(c) after to the preset reaction time, flask is taken out, and terminate reaction.
(d) it is cooled to room temperature to product in flask, vacuum filter is carried out to product, obtains filtrate and filter residue.
(e) filter residue obtained is cleaned with deionized water, and is detected with barium chloride, until liquid is no longer muddy,
It washs to neutrality.Filter residue is subjected to constituent analysis, wherein lignin content is 16.9%.
(f) obtained filtrate being diluted, until being diluted to acid concentration is 10%, stands 30min, solution becomes cloudy,
There is solid precipitation.Again with being filtered, solid is filtered out.And solid is dried, weighing and calculating is molten
Produce rate is 48.33% out
Embodiment 4:
(a) according to p-methyl benzenesulfonic acid: formic acid is the condition of 5:1, takes 97.2365 grams of the p-methyl benzenesulfonic acid, mass concentration to be
88% formic acid weighs 22.1290 grams, measures 50ml deionized water in the flask of 500ml, configures pair of 70% mass concentration
Toluenesulfonic acid-formic acid solution heats p-methyl benzenesulfonic acid-formic acid solution.
(b) 80 DEG C are heated to p-methyl benzenesulfonic acid-formic acid solution, 5 grams of poplar sawdusts, the size of poplar sawdust is then added
For 30~50 mesh, flask is put into 100rpm thermostatic control oscillator vibration, 20 minute reaction time was set, starts to react.
(c) after to the preset reaction time, flask is taken out, and terminate reaction.
(d) it is cooled to room temperature to product in flask, vacuum filter is carried out to product, obtains filtrate and filter residue.
(e) filter residue obtained is cleaned with deionized water, and is detected with barium chloride, until liquid is no longer muddy,
It washs to neutrality.Filter residue is subjected to constituent analysis, wherein lignin content is 11.47%.
(f) obtained filtrate being diluted, until being diluted to acid concentration is 10%, stands 30min, solution becomes cloudy,
There is solid precipitation.Again with being filtered, solid is filtered out.And solid is dried, weighing and calculating is molten
Object (lignin) yield is 83.15% out
Step (e) is diluted acid solution with deionized water, and dilute strength is that the mass concentration of p-methyl benzenesulfonic acid is 11%
~5%.Dilute strength is different, and lignin granular size is different, and granular size is 300 nanometers~3000 nanometers.Dilute strength is bigger,
Particle is bigger.
Embodiment 5: the present embodiment isolated lignin method the following steps are included:
(a) according to p-methyl benzenesulfonic acid: formic acid is the condition of 10:1, takes 181.8236 grams of the p-methyl benzenesulfonic acid, mass concentration to be
88% formic acid weighs 20.7864 grams, measures 50ml deionized water in the flask of 500ml, configures pair of 80% mass concentration
Toluenesulfonic acid-formic acid solution heats p-methyl benzenesulfonic acid-formic acid solution.
(b) 80 DEG C are heated to p-methyl benzenesulfonic acid-formic acid solution, 5 grams of poplar sawdusts, the size of poplar sawdust is then added
For 30~50 mesh, flask is put into 100rpm thermostatic control oscillator vibration, 10 minute reaction time was set, starts to react.
(c) after to the preset reaction time, flask is taken out, and terminate reaction.
(d) it is cooled to room temperature to product in flask, vacuum filter is carried out to product, obtains filtrate and filter residue.
(e) filter residue obtained is cleaned with deionized water, and is detected with barium chloride, until liquid is no longer muddy,
It washs to neutrality.Constituent analysis is carried out to filter residue, wherein lignin content is 19.42%.
(f) obtained filtrate being diluted, until being diluted to acid concentration is 10%, stands 30min, solution becomes cloudy,
There is solid precipitation.Again with being filtered, solid is filtered out.And solid is dried, weighing and calculating is molten
Object (lignin) yield is 68.93% out
Embodiment 6: the present embodiment isolated lignin method the following steps are included:
(a) according to p-methyl benzenesulfonic acid: formic acid is the condition of 20:1, takes 428.5422 grams of the p-methyl benzenesulfonic acid, mass concentration to be
88% formic acid weighs 24.3566 grams, measures 50ml deionized water in the flask of 500ml, configures pair of 90% mass concentration
Toluenesulfonic acid-formic acid solution heats p-methyl benzenesulfonic acid-formic acid solution.
(b) 80 DEG C are heated to p-methyl benzenesulfonic acid-formic acid solution, 5 grams of poplar sawdusts, the size of poplar sawdust is then added
For 30~50 mesh, flask is put into 100rpm thermostatic control oscillator vibration, 20 minute reaction time was set, starts to react.
(c) after to the preset reaction time, flask is taken out, and terminate reaction.
(d) it is cooled to room temperature to product in flask, vacuum filter is carried out to product, obtains filtrate and filter residue.
(e) filter residue obtained is cleaned with deionized water, and is detected with barium chloride, until liquid is no longer muddy,
It washs to neutrality.Filter residue is subjected to constituent analysis, wherein lignin content is 18.19%.
(f) obtained filtrate being diluted, until being diluted to acid concentration is 10%, stands 30min, solution becomes cloudy,
There is solid precipitation.Again with being filtered, solid is filtered out.And solid is dried, weighing and calculating is molten
Object (lignin) yield is 60.16% out.
Embodiment 3-6 acquired results are available, when p-methyl benzenesulfonic acid and formic acid are 5:1, mass concentration 70%, temperature
It is 80 DEG C, when the reaction time is 20 minutes, lignin the amount of dissolution is most, is optimal case.
Infrared analysis is carried out to the lignin extracted in filtrate in embodiment 4, as a result such as Fig. 1.The experimental results showed that toluene
The lignin of sulfonic acid processing, 3417cm-1The stretching vibration enhancing for locating O-H key in phenolic hydroxyl group and alcoholic extract hydroxyl group, compared with acid-insoluble lignin,
Peak position shifts, by 3422cm-1It is displaced to 3417cm-1.The C-H vibration of methyl, methylene increases in lignin at 2924cm-1
By force, peak position is displaced to 2924cm-1 by 2934cm-1.It is the C in non-conjugated ketone, carbonyls and ester group at 1714cm-1
The enhancing of=O stretching vibration bands of a spectrum.1400cm-1 to 1497cm-1 aromatic backbone vibrational band enhance.Lilac at 1327cm-1
C-O vibration disappearance in guaiacyl OCH at nuclear vibration and 1270cm-1.The ehter bond C-H vibration of S type lignin subtracts at 1231cm-1
It is weak, there is the C-O-C stretching vibration of 1180cm-1 absorption peak ehter bond.There is 567cm-1 to 814cm-1 absorption peak.
X-ray diffraction (XRD) analysis is carried out to the filter residue in the fiber and embodiment 4 in embodiment 2, it is real as a result such as Fig. 2
Test the result shows that, two kinds of cellulose peak positions are constant, and the cellulose peak value obtained after the processing of p-methyl benzenesulfonic acid-formic acid reduces very
Few, crystallinity still keeps higher.
Scanning electron microscope is done to the filter residue fiber in poplar sawdust, 2 fiber of embodiment and embodiment 4, as a result such as Fig. 3.Comparison
The form that two kinds of isolated lignins obtain fiber can be seen that by p-methyl benzenesulfonic acid-formic acid treated fiber filter residue structure more
There is interformational sliding and peeling fluffiness, illustrate by first in Gabon pine, fibrocyte layer especially compound middle lamella
Benzene sulfonic acid-formic acid treatment process can not only lignin between fast degradation fibrocyte, while can also effectively permeate and fibre of degrading
Intracellular lignin is tieed up, delignification effect is higher.
Outside divided by above-described embodiment, the present invention can also have other embodiments.Above-described embodiment is only exemplary implementation
Example, is not used in the limitation present invention, all technical solutions formed using equivalent substitute or equivalent transformation, the present invention claims
Protection scope.
Claims (7)
1. a kind of method for separating wood lignin, which is characterized in that the method comprises the following steps that
1) wood powder is added in 60 DEG C -90 DEG C of toluenesulfonic acid-formic acid solution and is reacted；
2) after reaction, separating filtrate and filter residue；Filtrate is diluted with deionized water, generates precipitating, precipitating is filtered
Lignin and acid pickle are obtained out.
2. the method as described in claim 1, which is characterized in that the toluenesulfonic acid-formic acid solution, wherein toluenesulfonic acid and
The volume ratio of formic acid is 1-20:1.
3. the method as described in claim 1, which is characterized in that the toluenesulfonic acid-formic acid solution, wherein toluenesulfonic acid and
The volume ratio of formic acid is 5:1.
4. the method as described in claim 1, which is characterized in that the reaction in the step 1) is under the conditions of water bath with thermostatic control
Carry out revolving reaction or oscillating reactions.
5. the method as described in claim 1, which is characterized in that the wood powder is cotton wood powder.
6. the method as described in claim 1, which is characterized in that the spent acid first passes through distillation, recycles formic acid, then by cold
But concentration and recovery p-methyl benzenesulfonic acid again.
7. the method as described in claim 1, which is characterized in that in the step 2), the usage amount of deionized water is to make to filter
The ph value of liquid is 7.0-7.5.
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