CN109806846A - Tremella and hickory chick common fermentation sesame stalk remove indigo method - Google Patents
Tremella and hickory chick common fermentation sesame stalk remove indigo method Download PDFInfo
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Abstract
The present invention relates to a kind of tremellas and hickory chick common fermentation sesame stalk to remove indigo method, the following steps are included: tremella bacterial strain and hickory chick bacterial strain are at 25-28 DEG C of humidity 70-80% of temperature, it is cultivated on potato dextrose agar plate, punching obtains 1.0 cm bacterium piece of diameter；It is sieved after the washed drying and crushing of stalk, obtain dye sorbent raw material, weigh 10.0-30.0g raw material, distilled water is added in raw material and water ratio 1:3-1:5 (g/mL), addition inducer sterilizes at 121 DEG C to be cooled to room temperature after 30min, inoculating strain, every kind of 2 ferfas piece of strain inoculated ferment under 25-28 DEG C of humidity 75%；Matrix obtains dye sorbent through drying and crushing after fermentation；20.0 g of adsorbent is taken, 200 mg/L, pH 6.0 of dye strength is added to, in 0 mol/L aqueous solution of NaCl concentration according to 1:150 solid-to-liquid ratio (m/v, g/mL), is absorbed and filter at 30 DEG C of 200 r/min of revolving speed of temperature；Adsorbent adsorb dyestuff it is indigo after air-dry, cooling is calcined at 500-600 DEG C, ash content returning to the field, it is green process technology that it is easy to operate, low in cost that the present invention removes indigo method.
Description
Technical field
The invention belongs to industrial waste water treatments, and in particular to a kind of to utilize tremella and hickory chick common fermentation sesame
Stalk prepare dye sorbent absorption dyestuff it is indigo come reach effectively remove Wastewater Dyes pollutant tremella and hickory chick it is total
Fermented Semen Sesami stalk removes indigo method；Tremella and hickory chick common fermentation sesame stalk prepare dye sorbent, and adsorbent is inhaled
It is ashed returning to the field after attached dye is indigo, eliminates harmful dyestuff and accumulates in the environment.
Background technique
Waste water from dyestuff is one of the industrial wastewater for being difficult to administer, and the removal of Wastewater Dyes pollutant is to administer waste water from dyestuff
Critical issue.
Indigo (Indigo carmine) is most ancient one of dyestuff, is widely used in plastics printing and dyeing, textile printing and dyeing etc.,
As cowboy prints and dyes.However, during producing and application is indigo, along with the generation of a large amount of colorful wastewaters.It goes to remove water at present
Indigo method has absorption method in body, and photocatalysis and microbial degradation etc., wherein absorption method has inexpensive and easy-operating excellent
Point.Sesame is one of China's major oil crops, and the resourceful but processing technique of sesame stalk is not perfect, if sesame straw
Stalk is directly abandoned or is burned, and is resulted in waste of resources and environmental pollution.Select abundance, low-cost sesame stalk as suction
Attached dose, by indigo in absorption method removal water body, with economic benefit and environmental benefit.However, sesame stalk is wood fibre
Cellulosic biomass has structure stubbornness and chemically inert characteristic, haves the shortcomings that small (the Li Huixing microbial method of Dye Adsorption amount
Decoloration printing dye and its Mechanism Study [D], Southern Yangtze University's doctoral thesis, 2015).
Stalk modification can destroy its obstinate structure, modification and/or introduce chemical functional group, can significantly improve absorption
Amount.Currently, the main method of modifying of sesame stalk is chemical method, if Li Hui magnitude is using the modified sesame stalk of NaOH, it is improved
Adsorbance (Li H X, Zhang R J, Tang L, the et al. Congo red adsorption Congo red to dyestuff
capacity of lignocellulosic biomass by sodium hydroxide treatment.[J]. Asian
Journal of Chemistry, 2015,27 (7): 2373-2378.).Wu Tao etc. is used first using sesame stalk as raw material
Amylase and protease are digested, then with KOH, dilute H2SO4, urea chemically react, prepare adsorbent material.(Wu Tao
Sesame stalk adsorbent material and preparation method thereof, CN104028234A [P] 2014.).However, chemical method is modified sesame stalk
The chemical reagent such as acid, alkali processing stalk need to be used by preparing adsorbent, led to increased costs, generated secondary pollution problems.
Whiterot fungi by the penetration capacity of its mycelia, extracellular cellulolytic enzyme (cellulase, hemicellulase etc.) and
The secretion capacity of lignin-degrading enzymes (laccase, manganese peroxidase, lignin peroxidase etc.), can be with depolymerization and degradation straw
Stalk achievees the purpose that modified straw.Whiterot fungi is inoculated in stalk, is fermented under the conditions ofs certain temperature, humidity etc., bacterial strain with
Stalk is that substrate is grown and is metabolized, so that the chemical functional group (- OH ,-NH and C=O etc.) for adsorbing dyestuff in stalk becomes
Change, the surface of stalk is more coarse, and hole becomes larger.In addition, using interaction and substrate otherness between whiterot fungi, selection
Different whiterot fungis are combined, and can change the metabolic characteristic of bacterial strain by whiterot fungi co-fermentation technology, improve thalli growth speed
Rate and secretase ability.(section successor, Zhu Liping, tri- kinds of whiterot fungis of Yao Yueliang and combinations thereof strain lignin-degrading enzymes ratio
Compared with research [J] fungus journal, 2009,28 (4): 577-583；Elisashvili V, Kachlishvili E.
Physiological regulation of laccase and manganese peroxidase production by
White-rot Basidiomycetes [J] Journal of Biotechnology, 2009,144 (1): 37-42.).
Preparing dye sorbent using whiterot fungi common fermentation stalk is green process technology, have the characteristics that low cost, it is without secondary pollution,
Application prospect is boundless.
Summary of the invention
A kind of tremella and hickory chick common fermentation are provided it is an object of the invention to overcome the deficiencies in the prior art
Sesame stalk removes indigo method；On the basis of whiterot fungi bacterial strain screening, tremella bacterium and hickory chick common fermentation sesame are selected
Stalk prepares dye sorbent, and adsorbent adsorbs the indigo rear ashing returning to the field of dyestuff.The white rot bacteria strain of experiment screening of the present invention,
It buys in Chinese industrial Microbiological Culture Collection administrative center.Strain is mushroom respectivelyLentinulaSp.(bacterium numbering: CICC
14031), black fungusAuricularia auricula(strain number: CICC 14008), Gleoesterum incarnatumGloeostereum incarnatum(strain number: CICC 14024), hickory chickMorchellaSp.(strain number: CICC 14033), tremellaTremellafuciformis(strain number: CICC 50179), Trametes gallicaTrametes hirsuta(strain number:
CICC 2671) and Cordyceps militarisCordyceps militaris(strain number: CICC 14013).
The object of the present invention is achieved like this:
A kind of tremella and hickory chick common fermentation sesame stalk remove indigo method, comprising the following steps:
Step 1), white rot bacteria strain are under conditions of 25-28 DEG C of temperature, humidity 70-80%, in potato dextrose agar plate
It after upper culture 7-10 days, is punched on agar plate using the punch of 1.0 cm of diameter, obtains the bacterium piece of 1.0 cm of diameter；
Step 2, stalk be washed, it is dry, smash it through 20-60 mesh, obtain the raw material for being used to prepare dye sorbent；
Step 3) weighs 10.0-30.0g raw materials, and distilled water is added according to the ratio 1:3-1:5 (g/mL) of raw material and water, adds
It being cooled to room temperature after sterilizing 30min at 121 DEG C after adding inducer, is inoculated with whiterot fungi, every kind of whiterot fungi is inoculated with 2 ferfas pieces,
25-28 DEG C, cultivation and fermentation 10-15 days under conditions of humidity 75%；
After step 4), fermentation matrix through drying, smash it through 40 meshes, dye sorbent is prepared；
Step 5) after dye sorbent is prepared, adsorbs dyestuff indigo under the following conditions: weighing the adsorbent being prepared
20.0 g are added to 200 mg/L, pH 6.0 of dye strength, NaCl concentration 0 according to the solid-to-liquid ratio (m/v, g/mL) of 1:150
It in the aqueous solution of mol/L, is filtered after adsorbing 4 h under conditions of 30 DEG C of adsorption temp, 200 r/min of speed of agitator, calculates and inhale
Attached amount (mg/g)；
Natural air drying 36-48 h after step 6), adsorbent absorption dyestuff are indigo, calcines 4.0-6.0h at 500-600 DEG C, natural
It is cooling, obtain returning to the field after ash content.
Whiterot fungi described in step 1) is hickory chick and tremella bacterium.
Stalk described in step 2 is sesame stalk.
Addition inducer described in step 3) is addition 72.5 mM of acetic acid, Cu in every kilogram of stalk2+81.8mM
With alkaline 27.9 g of lignin, i.e. 72.5 mM/kg, Cu of acetic acid2+27.9 g/kg of 81.8mM/kg and alkaline lignin.
In the present invention, adsorbance (mg/g) calculation formula is (C0-C)×V/m；C in formula0It is indigo initial in solution
Concentration (mg/L), C are that indigo concentration (mg/L), V are liquor capacity (L) in solution after adsorbing, and m is adsorbent mass (g).
The present invention has following good effect:
The experimentation and data of verification the verifying results of the present invention are as follows:
1, whiterot fungi: 7 kinds of whiterot fungi (mushrooms is cultivatedLentinulaSp., black fungusAuricularia auricula, the tough leather of glue
BacteriumGloeostereum incarnatum, hickory chickMorchellaSp., tremellaTremella fuciformis, Trametes gallicaTrametes hirsutaAnd Cordyceps militarisCordyceps militaris) bacterial strain is respectively in 28 DEG C of temperature, the condition of humidity 75%
Under, after being cultivated 10 days on potato dextrose agar plate, punched on agar plate using the punch of 1.0 cm of diameter,
Obtain the bacterium piece of 1.0 cm of diameter；
2, pre-process sesame stalk: stalk is washed, it is dry, smash it through 40 meshes, obtain being used to prepare dye sorbent
Raw material；
3, whiterot fungi common fermentation sesame stalk: weighing 20.0g stalk, and distilled water is added according to material-water ratio 1:5 (g/mL),
It is cooled to room temperature after sterilizing 30min at 121 DEG C, is inoculated with 2 kinds of different whiterot fungis, every kind of whiterot fungi is inoculated with 2 ferfas pieces, 25
DEG C, humidity is fermented 14 days under conditions of being 75%.
4, prepare dye sorbent: after fermentation matrix through drying, smash it through 40 meshes, obtain dye sorbent.
5, it adsorbs dyestuff: after dye sorbent is prepared, it is indigo to adsorb dyestuff under the following conditions: weighing and is prepared
20.0 g of adsorbent, be added to 200 mg/L, pH 6.0 of dye strength, NaCl according to the solid-to-liquid ratio (m/v, g/mL) of 1:150
In the aqueous solution of 0 mol/L of concentration, filtered after adsorbing 4 h under conditions of 30 DEG C of adsorption temp, 200 r/min of speed of agitator,
Calculate adsorbance.
6, returning to the field after being ashed: adsorbent adsorbs dyestuff 48 h of indigo rear natural air drying, and 5.0h is calcined at 540 DEG C, natural
It is cooling, obtain returning to the field after ash content.
The advance of dye sorbent is prepared for display whiterot fungi common fermentation sesame stalk, is used in verification process of the present invention
7 kinds of whiterot fungi (mushroomsLentinulaSp., black fungusAuricularia auricula, Gleoesterum incarnatumGloeostereum incarnatum, hickory chickMorchellaSp., tremellaTremella fuciformis, Trametes gallicaTrametes hirsutaAnd Cordyceps militarisCordyceps militaris) under the above conditions, by the independent fermented Semen Sesami stalk of whiterot fungi,
That is: 20.0g stalk is weighed, distilled water is added according to material-water ratio 1:5 (g/mL), it is cooling after the 30min that sterilizes at 121 DEG C
To room temperature, it is inoculated with a kind of whiterot fungi, every kind of whiterot fungi is inoculated with 4 ferfas pieces, and at 25 DEG C, humidity is fermented 14 days under conditions of being 75%.
After fermentation matrix through drying, smash it through 40 meshes, prepare dye sorbent.
The independent fermented Semen Sesami stalk of comparative analysis sesame stalk raw material, whiterot fungi prepares dye sorbent, whiterot fungi is sent out altogether
Ferment sesame stalk prepares dye sorbent, and the different adsorbents adsorbance indigo to dyestuff is prepared in the case of these three, knot
Fruit is as shown in table 1.
It can be seen that sesame stalk raw material is 21.90 mg/g, the independent fermented Semen Sesami straw of whiterot fungi to indigo adsorbance
Stalk can be improved adsorbance, wherein tremellaTremella fuciformisThe effect of fermented Semen Sesami stalk is preferable, and adsorbance is
The effect of 29.07 mg/g, whiterot fungi common fermentation sesame stalk are more preferable, wherein hickory chickMorchellaAnd tremella sp.Tremella fuciformisAfter common fermentation sesame stalk, adsorbance reaches 40.87 mg/g, is compared to sesame stalk original
Material, improves 86.62% to indigo adsorbance.
The different adsorbents of table 1 are to indigo adsorbance
Hickory chickMorchellaAnd tremella sp.Tremella fuciformisCommon fermentation sesame stalk, in growth metabolism process
In, the secretion capacity of penetration capacity and ectoenzyme by its mycelia, depolymerization and degrading straw are improved to the indigo absorption of dyestuff
Amount.
Since whiterot fungi growth and secretase are significantly affected by inducer, using adsorbance as index, further use
Experiment of single factor investigates the influence of induction species and concentration, as a result sees Fig. 2-Fig. 7.
Fig. 2-Fig. 7 is influence of the different inducers to adsorbance, the results showed that alkaline lignin, guaiacol, acetic acid,
Cu2+Adsorbance can be improved with resveratrol, however hydrogen peroxide reduces adsorbance, this is because hydrogen peroxide is a kind of strong
Oxidant inhibits the growth and metabolism of bacterial strain during the fermentation.On the basis of experiment of single factor result, select effect compared with
Alkaline lignin, acetic acid and Cu good, price is less expensive2+Three kinds of inducers, using the Box-Behnken scheme of Response Surface Method
It designs (table 2) and investigates the reciprocation of inducer, optimization inducer concentration.Box-Behnken conceptual design result (table 3) warp
Minitab software is analyzed to obtain: acetic acid concentration (X1), acetic acid concentration quadratic term (X1 2), Cu2+Concentration quadratic term (X2 2), acetic acid it is dense
Reciprocation (the X of degree and alkaline lignin concentration1×X3) on adsorbance have it is extremely significant influence (p< 0.01), acetic acid concentration (X1)
And Cu2+Concentration (X2) reciprocation adsorbance is had a significant impact (p< 0.05) (table 4).
The optimal combination of inducer is acetic acid 72.5mM/kg, Cu2+27.9 g/kg of 81.8mM/kg and alkaline lignin, warp
Under optimum combination condition, adsorbance reaches 74.25mg/g for experimental verification.
The Box-Behnken conceptual design table of the optimization inducer concentration of table 2
Adsorbance under the different inducer concentration of table 3
| Serial number | X1 | X2 | X3 | Adsorbance (mg/g) |
| 1 | -1 | -1 | 0 | 54.36 |
| 2 | -1 | 1 | 0 | 49.90 |
| 3 | 1 | -1 | 0 | 59.06 |
| 4 | 1 | 1 | 0 | 65.84 |
| 5 | 0 | -1 | -1 | 61.89 |
| 6 | 0 | -1 | 1 | 58.32 |
| 7 | 0 | 1 | -1 | 60.30 |
| 8 | 0 | 1 | 1 | 63.33 |
| 9 | -1 | 0 | -1 | 53.02 |
| 10 | 1 | 0 | -1 | 70.34 |
| 11 | -1 | 0 | 1 | 66.32 |
| 12 | 1 | 0 | 1 | 68.05 |
| 13 | 0 | 0 | 0 | 72.30 |
| 14 | 0 | 0 | 0 | 73.42 |
| 15 | 0 | 0 | 0 | 73.01 |
4 analysis of variance table of table
| Factor | Freedom degree | pValue |
| X1 | 1 | <0.01* |
| X2 | 1 | 0.33 |
| X3 | 1 | 0.11 |
| X1*X1 | 1 | <0.01** |
| X2*X2 | 1 | <0.01** |
| X3*X3 | 1 | 0.06 |
| X1*X2 | 1 | <0.05* |
| X1*X3 | 1 | <0.01** |
| X2*X3 | 1 | 0.14 |
| Lack of fit | 3 | 0.06 |
*p< 0.05 indicates significant; **p< 0.01 indicates extremely significant
Therefore a kind of tremella provided by the invention and hickory chick common fermentation sesame stalk remove indigo method, including main step
Suddenly have: pretreatment sesame stalk, tremella and hickory chick common fermentation sesame stalk prepare dye sorbent, adds in fermentation process and lures
Lead object acetic acid 72.5 mM/kg, Cu2+27.9 g/kg of 81.8mM/kg and alkaline lignin, adsorbent adsorb the indigo rear ashing of dyestuff
Returning to the field.Preparing dye sorbent using whiterot fungi common fermentation sesame stalk has the characteristics that low cost, without secondary pollution, adsorbent
The indigo rear ashing returning to the field of dyestuff is adsorbed, dyestuff is completely eliminated and accumulates in the environment；The present invention is sent out altogether using tremella and hickory chick
It is easy to operate, low in cost that ferment sesame stalk removes indigo method, is green process technology.
Detailed description of the invention
Fig. 1 is the process step of the invention figure.
Fig. 2 is influence diagram of the alkaline lignin inducer to adsorbance.
Fig. 3 is influence diagram of the guaiacol inducer to adsorbance.
Fig. 4 is influence diagram of the acetic acid inducer to adsorbance.
Fig. 5 is Cu2+Influence diagram of the inducer to adsorbance.
Fig. 6 is influence diagram of the Resveratrol Inducing object to adsorbance.
Fig. 7 is influence diagram of the hydrogen peroxide-induced object to adsorbance.
Specific embodiment
Embodiment 1: as shown in Figure 1, a kind of tremella provided by the invention and the removal of hickory chick common fermentation sesame stalk are indigo
Method, comprising the following steps:
Step 1), culture whiterot fungi: 2 kinds of whiterot fungi (hickory chicksMorchellaSp., tremellaTremella fuciformis) bacterium
Strain, respectively under conditions of 25 DEG C of temperature, humidity 80%, after being cultivated 8 days on potato dextrose agar plate, using diameter
The punch of 1.0 cm punches on agar plate, obtains the bacterium piece of 1.0 cm of diameter；
Step 2, pretreatment sesame stalk: stalk is washed, it is dry, smash it through 20 meshes, obtain being used to prepare Dye Adsorption
The raw material of agent；
Step 3), whiterot fungi common fermentation sesame stalk: weighing 10.0g stalk, is added and steams according to material-water ratio 1:3 (g/ml)
Distilled water adds inducer acetic acid 72.5 mM/kg, Cu2+27.9 g/kg of 81.8mM/kg and alkaline lignin, sterilizes at 121 DEG C
It is cooled to room temperature after 30min.2 kinds of different whiterot fungis are inoculated with, every kind of whiterot fungi is inoculated with 2 ferfas pieces, at 28 DEG C, humidity 75%
Under conditions of ferment 10 days；
Step 4) prepares dye sorbent: after fermentation matrix through drying, smash it through 40 meshes, obtain dye sorbent；
Step 5), absorption dyestuff: it after dye sorbent is prepared, adsorbs under the following conditions indigo: weighing and be prepared
It is dense to be added to 200 mg/L, pH 6.0 of dye strength, NaCl according to the solid-to-liquid ratio (m/v, g/mL) of 1:150 by 20.0 g of adsorbent
It spends in the aqueous solution of 0 mol/L, is filtered after adsorbing 4 h under conditions of 30 DEG C of adsorption temp, 200 r/min of speed of agitator, counted
Calculation adsorption capacity is 74.04 mg/g；
Returning to the field after step 6), ashing: adsorbent adsorbs dyestuff 24 h of indigo rear natural air drying, and 6.0 h are calcined at 500 DEG C, from
It is so cooling, obtain returning to the field after ash content.
Embodiment 2: as shown in Figure 1, a kind of tremella provided by the invention and the removal of hickory chick common fermentation sesame stalk are indigo
Method, comprising the following steps:
Step 1), culture whiterot fungi: 2 kinds of whiterot fungi (hickory chicksMorchellaSp., tremellaTremella fuciformis) bacterium
Strain is respectively under conditions of 28 DEG C of temperature, humidity 70%, after cultivating 7 days on potato dextrose agar plate, using diameter
The punch of 1.0 cm punches on agar plate, obtains the bacterium piece of 1.0 cm of diameter；Step 2, pretreatment sesame stalk: straw
Stalk is washed, it is dry, smash it through 60 meshes, obtain the raw material for being used to prepare dye sorbent；
Step 3), whiterot fungi common fermentation sesame stalk: weighing 30.0g stalk, is added and steams according to material-water ratio 1:4 (g/mL)
Distilled water adds inducer acetic acid 72.5 mM/kg, Cu2+27.9 g/kg of 81.8mM/kg and alkaline lignin, sterilizes at 121 DEG C
It is cooled to room temperature after 30min.It is inoculated with 2 kinds of different whiterot fungis respectively, every kind of whiterot fungi is inoculated with 2 ferfas pieces, and at 27 DEG C, humidity is
It ferments 15 days under conditions of 75%；
Step 4) prepares dye sorbent: after fermentation matrix through drying, smash it through 40 meshes, obtain dye sorbent；
Step 5), absorption dyestuff: it after dye sorbent is prepared, adsorbs under the following conditions indigo: weighing and be prepared
It is dense to be added to 200 mg/L, pH 6.0 of dye strength, NaCl according to the solid-to-liquid ratio (m/v, g/mL) of 1:150 by 20.0 g of adsorbent
It spends in the aqueous solution of 0 mol/L, is filtered after adsorbing 4 h under conditions of 30 DEG C of adsorption temp, 200 r/min of speed of agitator, counted
Calculation adsorption capacity is 73.67 mg/g；
Returning to the field after step 6), ashing: adsorbent adsorbs dyestuff 36 h of indigo rear natural air drying, and 4.0 h are calcined at 600 DEG C, from
It is so cooling, obtain returning to the field after ash content.
Claims (4)
1. a kind of tremella and hickory chick common fermentation sesame stalk remove indigo method, which comprises the following steps:
Step 1), white rot bacteria strain are under conditions of 25-28 DEG C of temperature, humidity 70-80%, in potato dextrose agar plate
It after upper culture 7-10 days, is punched on agar plate using the punch of 1.0 cm of diameter, obtains the bacterium piece of 1.0 cm of diameter；
Step 2, stalk be washed, it is dry, smash it through 20-60 mesh, obtain the raw material for being used to prepare dye sorbent；
Step 3) weighs 10.0-30.0g raw materials, and distilled water is added according to the ratio 1:3-1:5 (g/mL) of raw material and water, adds
It being cooled to room temperature after sterilizing 30min at 121 DEG C after adding inducer, is inoculated with whiterot fungi, every kind of whiterot fungi is inoculated with 2 ferfas pieces,
25-28 DEG C, cultivation and fermentation 10-15 days under conditions of humidity 75%；
After step 4), fermentation matrix through drying, smash it through 40 meshes, dye sorbent is prepared；
Step 5) after dye sorbent is prepared, is adsorbed indigo under the following conditions: weighing the adsorbent 20.0 being prepared
G is added to dye strength 200 mg/L, pH 6.0,0 mol/L of NaCl concentration according to the solid-to-liquid ratio (m/v, g/mL) of 1:150
It in aqueous solution, is filtered after adsorbing 4 h under conditions of 30 DEG C of adsorption temp, 200 r/min of speed of agitator, calculates adsorbance；
Natural air drying 36-48 h after step 6), adsorbent absorption dyestuff are indigo, calcines 4.0-6.0h at 500-600 DEG C, natural
It is cooling, obtain returning to the field after ash content.
2. a kind of tremella as described in claim 1 and hickory chick common fermentation sesame stalk remove indigo method, feature exists
In: the whiterot fungi described in step 1) is hickory chick and tremella bacterium.
3. a kind of tremella as described in claim 1 and hickory chick common fermentation sesame stalk remove indigo method, feature exists
In: the stalk described in step 2 is sesame stalk.
4. a kind of tremella as described in claim 1 and hickory chick common fermentation sesame stalk remove indigo method, feature exists
In: the addition inducer described in step 3) is addition 72.5 mM of acetic acid, Cu in every kilogram of stalk2+81.8mM and alkali
Property 27.9 g of lignin, i.e. 72.5 mM/kg, Cu of acetic acid2+27.9 g/kg of 81.8mM/kg and alkaline lignin.
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