CN104745638A - Method for co-producing organic solvent and hydrogen by using traditional Chinese medicine residues - Google Patents
Method for co-producing organic solvent and hydrogen by using traditional Chinese medicine residues Download PDFInfo
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- CN104745638A CN104745638A CN201510151675.0A CN201510151675A CN104745638A CN 104745638 A CN104745638 A CN 104745638A CN 201510151675 A CN201510151675 A CN 201510151675A CN 104745638 A CN104745638 A CN 104745638A
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- acid hydrolysis
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- 239000003814 drug Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000001257 hydrogen Substances 0.000 title claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000003960 organic solvent Substances 0.000 title claims abstract description 23
- 235000000346 sugar Nutrition 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000855 fermentation Methods 0.000 claims abstract description 14
- 230000004151 fermentation Effects 0.000 claims abstract description 14
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005695 Ammonium acetate Substances 0.000 claims abstract description 9
- 235000019257 ammonium acetate Nutrition 0.000 claims abstract description 9
- 229940043376 ammonium acetate Drugs 0.000 claims abstract description 9
- 239000002893 slag Substances 0.000 claims description 61
- 239000007788 liquid Substances 0.000 claims description 36
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- 150000008163 sugars Chemical class 0.000 claims description 14
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 13
- 239000001117 sulphuric acid Substances 0.000 claims description 13
- 235000011149 sulphuric acid Nutrition 0.000 claims description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 11
- 239000000920 calcium hydroxide Substances 0.000 claims description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- 239000000284 extract Substances 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 230000001580 bacterial effect Effects 0.000 claims description 8
- 239000004615 ingredient Substances 0.000 claims description 8
- 230000001256 tonic effect Effects 0.000 claims description 8
- 230000001954 sterilising effect Effects 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000002054 inoculum Substances 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 241000193454 Clostridium beijerinckii Species 0.000 claims description 3
- 238000011081 inoculation Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 abstract description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 8
- 239000000413 hydrolysate Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000001784 detoxification Methods 0.000 abstract description 3
- 239000011790 ferrous sulphate Substances 0.000 abstract description 3
- 235000003891 ferrous sulphate Nutrition 0.000 abstract description 3
- 239000001963 growth medium Substances 0.000 abstract description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229940010514 ammonium ferrous sulfate Drugs 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 229940126680 traditional chinese medicines Drugs 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000002609 medium Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- LWFUFLREGJMOIZ-UHFFFAOYSA-N 3,5-dinitrosalicylic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O LWFUFLREGJMOIZ-UHFFFAOYSA-N 0.000 description 4
- 150000008442 polyphenolic compounds Chemical class 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- 241000193403 Clostridium Species 0.000 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 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011218 seed culture Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 241000411851 herbal medicine Species 0.000 description 2
- 235000012907 honey Nutrition 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 241000132012 Atractylodes Species 0.000 description 1
- 241000522254 Cassia Species 0.000 description 1
- 241001112695 Clostridiales Species 0.000 description 1
- 241000756943 Codonopsis Species 0.000 description 1
- 235000019750 Crude protein Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 239000009636 Huang Qi Substances 0.000 description 1
- 241000112528 Ligusticum striatum Species 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 244000170916 Paeonia officinalis Species 0.000 description 1
- 235000006484 Paeonia officinalis Nutrition 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 244000197580 Poria cocos Species 0.000 description 1
- 235000008599 Poria cocos Nutrition 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000009264 composting Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 235000019629 palatability Nutrition 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a method for co-producing organic solvent and hydrogen by using traditional Chinese medicine residues. The method uses the traditional Chinese medicine residue hydrolysate which can be directly used for fermentation raw materials without detoxification treatment, and can ferment and produce butanol, acetone, ethanol and hydrogen only by adding water, ammonium acetate and ferrous sulfate without adding other substances when the traditional Chinese medicine residue hydrolysate is used for preparing a fermentation culture medium, wherein the total solvent yield can reach 23g/L and 16g/L of butanol, the total solvent sugar yield can reach 0.40g/g, and the hydrogen yield can reach 6100 mL/L. The invention is beneficial to solving the problem of environmental pollution caused by the accumulation of the traditional Chinese medicine residues and improving the resource utilization level of the traditional Chinese medicine on one hand, and can be used for producing organic solvents commonly used in the production of the traditional Chinese medicines such as butanol, acetone, ethanol and the like and coproducing hydrogen as an energy source on the other hand.
Description
Technical field
Patent of the present invention relates to a kind of method utilizing Chinese medicine slag coproduction organic solvent and hydrogen, belongs to biomass recovery and utilization technology field and fermentation engineering field.
Background technology
Chinese Medicine Industry is the important component part of China's pharmaceutical industry, a large amount of Chinese patent medicine preparation all can be had to put on market every year, but due to Chinese medicine preparation mainly extract in herbal medicine some effective constituent, therefore large number of biological matter is not utilized, and creates a large amount of discarded Chinese medicine residues.Owing to containing a large amount of organic and moisture in Chinese medicine residue, process very easily corrupt smelly not in time, can not pile up for a long time.Traditional burning, bury and process not only contaminate environment, also cause the serious wasting of resources.Owing to being rich in organic matter in Chinese medicine slag, also containing various trace element, can be used for edible fungus culturing and composting etc., but these methods need the treatment cycle of several months and take tract, Chinese medicine slag is used for fodder additives and also has report, but the most of dregs of a decoction are pained, and palatability is poor, therefore directly to acquire a certain degree of difficulty as fodder additives tool.
Propyl carbinol, ethanol, acetone are organic solvents conventional during Chinese herbal medicine extracting is refined, and owing to having certain volatility, have certain loss aborning.Produce solvent clostridium and can prepare propyl carbinol, ethanol, acetone by anaerobically fermenting carbohydrate simultaneously, also can accumulate a large amount of hydrogen in product dissolving agent process simultaneously, hydrogen is a kind of clean green energy resource, unit calorific value is up to 121KJ/g, and only produce water molecules and pollution-free during burning, there is certain utility value.Although solvent fermentation has realized suitability for industrialized production for many years, but use the grain such as cassava, corn raw material to cause cost higher, therefore prepare organic solvent with abandoned biomass resource cheap and easy to get and be subject to extensive concern, utilize the agriculture and forestry organic waste material such as stalk, corn cob to prepare acidolysis liquid glucose and have been reported for clostridium anaerobically fermenting production organic solvent.Be rich in the multiple organic matters such as polysaccharide, crude protein and VITAMIN in Chinese medicine slag, also contain the inorganic elementss such as N, P, K, and these meet primary condition needed for fermentable.But current Chinese medicine slag is fermenting raw materials prepares organic solvent not yet open report; therefore Chinese medicine slag hydrolysis is prepared into fermentable liquid glucose; related products is prepared for fermentable; can turn waste into wealth; improve the producing level of Chinese material medicine resource, minimizing is consumed, protection of the environment is significant.
Summary of the invention
Wood fibre hydrolysis liquid for Chinese medicine slag contaminate environment and non-detoxification is used for the problem of clostridial fermentation weak effect, a kind of dregs of a decoction are the object of the present invention is to provide to recycle the method for coproduction organic solvent and biological hydrogen, to realize the recycling of the discarded dregs of a decoction, and provide a kind of can as the novel cheap raw material of co-producing bio mass-energy source butanols and hydrogen.
For achieving the above object, the technical solution used in the present invention is as follows:
Utilize a method for Chinese medicine slag coproduction organic solvent and hydrogen, it comprises the following steps:
(1) collection of Chinese medicine slag and pre-treatment: after Chinese medicine slag is collected, dry and pulverize to obtain Chinese medicine slag powder;
(2) preparation of Chinese medicine slag dilute acid hydrolysis liquid glucose: add dilute sulphuric acid in Chinese medicine slag powder, carries out pyrohydrolysis, and after hydrolysis, filtration residue obtains filtrate; Add calcium hydroxide neutralization filtrate, again cross and filter calcium sulfate precipitation, obtain Chinese medicine slag dilute acid hydrolysis liquid;
(3) preparation of Chinese medicine slag dilute acid hydrolysis liquid fermention medium: with water, FeSO
47H
2o and ammonium acetate preparation substratum, for subsequent use after sterilizing; PH value to 6.5 ~ 7.0 of the Chinese medicine slag dilute acid hydrolysis liquid that regulating step (2) obtains, add substratum after sterilizing, are mixed with the fermention medium that total reducing sugars concentration is 30 ~ 60g/L;
(4) Chinese medicine slag dilute acid hydrolysis liquid fermentation: by inoculum size 10%V/V the inoculation in advance fermention medium of cultured bacterial classification after sterilizing, in 35 DEG C of anaerobically fermenting 48 ~ 72h.
In step (1), described Chinese medicine slag is the pharmacy residue of Chinese patent medicine tonic semifluid extract of ten ingredients.Described tonic semifluid extract of ten ingredients, its former medicine is primarily of taste Chinese medicine compositions such as Radix Codonopsis, the bighead atractylodes rhizome (stir-fry), Poria cocos, Radix Glycyrrhizae (honey is processed), Radix Angelicae Sinensis, Ligusticum wallichii, the root of herbaceous peony (wine stir-fry), Radix Rehmanniae Preparata, the Radix Astragali (honey is processed), Chinese cassia trees.
In step (1), described Chinese medicine slag powder diameter is 30 ~ 40 orders.
In step (2), described dilute sulphuric acid is the dilute sulphuric acid of concentration 1 ~ 3%V/V (preferably 2 ~ 3%V/V), the mass volume ratio (abbreviation solid-to-liquid ratio) of Chinese medicine slag powder and dilute sulphuric acid is 1g:4 ~ 6mL (preferred 1g:4 ~ 5mL), and described pyrohydrolysis is be hydrolyzed 90 ~ 150min (preferably 120 ~ 150min) under 115 ~ 120 DEG C of temperature condition.
In step (2), the condition of calcium hydroxide neutralization filtrate is adopted to be stir at 50 DEG C and add calcium hydroxide, be adjusted to pH4 ~ 6.
In step (2), the Chinese medicine slag dilute acid hydrolysis liquid obtained, wherein, total reducing sugars concentration is 39 ~ 70g/L, and glucose content is 21 ~ 39g/L.
In step (2), obtain Chinese medicine slag dilute acid hydrolysis liquid through concentration, being concentrated into total reducing sugars concentration is 100 ~ 120g/L, then carries out the program of step (3).
In step (3), add in the substratum of Chinese medicine slag dilute acid hydrolysis liquid, FeSO
47H
2the concentration of O is 0.01 ~ 0.5g/L, and the concentration of ammonium acetate is 2 ~ 3g/L.
In step (3), the NaOH aqueous solution or the HCl aqueous solution is used to regulate pH value to 6.5 ~ 7.0 of Chinese medicine slag dilute acid hydrolysis liquid.The preferred use NaOH aqueous solution of 2mol/L or the HCl aqueous solution of 2mol/L.
In step (3), the sterilising conditions adopted is 121 DEG C, and 15min is cooled to normal temperature subsequently.
In step (4), described bacterial classification is Bai Shi clostridium Clostridium beijerinckii IB4CCTCC M 2010310, and this bacterial strain has been disclosed in Chinese patent 201110020102.6 (plant height resistance bayesian clostridium and an application thereof).
Detection total reducing sugars method of the present invention is conventional DNS colorimetry.DNS preparation of reagents method: take 3,5-dinitrosalicylic acid (10 ± 0.1) g and be placed in about 600ml water, add sodium hydroxide 10g gradually, after 50 degree of stirred in water bath are dissolved, then adds Seignette salt 200g successively.Phenol (fumigating) 2g and sodium sulphite anhydrous 99.3 5g, after all dissolving clarification, is cooled to room temperature, and constant volume, to 1000mL, filters.Be stored in brown reagent bottle, use after dark place places 7 days.Concrete detection method: first with glucose as a standard thing, makes typical curve.Then get the dilute acid hydrolysis liquid 1mL after dilution 100 times, add pure water 2.5mL, DNS reagent 2.5mL, take pure water as contrast, under 540nm, survey absorbancy, thus draw dilute acid hydrolysis concentration of reduced sugar.
It is conventional forint phenol colorimetry that the present invention detects the anatoxic method of phenol, and the reagent adopted is forint phenol reagent and 100mL alkali lye (20g sodium carbonate+1.2g sodium tartrate is dissolved in the preparation of 100ml hot water).Concrete detection method: using Vanillin and tannin as the reference material of single phenol and polyphenol, make typical curve.After dilute acid hydrolysis liquid dilution pure water is diluted 200 times, being placed in 30 degree of water-bath preheating 10min, then first adding 5mL alkali lye, then add 0.5mL forint phenol reagent, continue heating 30 minutes, is survey absorbancy in comparison with 700nm with pure water.
The present invention detect acetone, ethanol, butanols method be vapor-phase chromatography, the produced total solvent that ferments in the present invention refers in particular to the concentration sum of acetone, ethanol, butanols three kinds of products.
The method that the present invention detects hydrogen is: adopt U.S. H
2hY-OPTIMATM 700 hydrogen gas sensor of Scan company, the hydrogen content in the accumulation volume of on-line checkingi fermentation gas, flow and gas.
Beneficial effect of the present invention is:
1, pile up corrupt easily contaminate environment and the problem of recycling approach existing defects for Chinese medicine slag, Chinese medicine slag dilute acid hydrolysis is prepared into the substratum that can be utilized by fermentable.
2, the process of Chinese medicine slag dilute acid hydrolysis liquid is simple, and hydrolysis cost is lower.
3, avoid the detoxification treatment step after hydrolyzed solution preparation, simplified operation, decrease sugar and lose and reduce processing cost.
4, in the hydrolyzed solution produced, glucose content accounts for about 60% of total reducing sugars, is conducive to microorganism and utilizes.
Only can add ferrous sulfate, ammonium acetate and Chinese medicine slag dilute acid hydrolysis liquid and other materials need not be added just can obtain good production performance when 5, preparing fermention medium.
6, the inventive method total solvent output can reach 23g/L, butanols 16g/L, and total solvent can reach 0.40g/g to sugared yield, and hydrogen output reaches 6100mL/L.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, the content described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
Below testing bacterial classification used is Bai Shi clostridium Clostridium beijerinckii IB4CCTCC M 2010310.
This bacterial classification needs to carry out seed culture in advance before fermenting, and its seed culture is cultivated and is: yeast powder 3g/L, peptone 5g/L, Zulkovsky starch 10g/L, ammonium acetate 2g/L, NaCl 2g/L, MgSO
43g/L, KH
2pO
41g/L, K
2hPO
41g/L, FeSO
47H
2o 0.1g/L, pH 6.0.Bacterial classification carries out secondary seed cultivation.I and II seed culture all adopts serum bottle to carry out Anaerobic culturel, inoculum size 5%, and after inoculation, logical sterile nitrogen 2min, cultivates 10h and 12h at 35 DEG C respectively.
Embodiment 1:
Take and dry and be crushed to 30 ~ 40 order pulverous tonic semifluid extract of ten ingredients dregs of a decoction 20g, adding 100ml concentration to is in the dilute sulphuric acid of 1 ~ 3% (V/V) (solid-to-liquid ratio 1:5), in 120 DEG C of hydrolysis 120min, filter and use deionized water wash residue to 100mL.Gained filtrate neutralizes pH4.0 ~ 5.0 with calcium hydroxide, and again filter and use deionized water wash residue to 100mL, gained filtrate is the dilute acid hydrolysis liquid of these dregs of a decoction, measures total reducing sugars, glucose, single phenol and polyphenol content wherein, as shown in table 1.
Chinese medicine slag is hydrolyzed under the different sulfuric acid concentration of table 1
Embodiment 2:
Take and dry and be crushed to the pulverous tonic semifluid extract of ten ingredients dregs of a decoction of 30 ~ 40 order to add sulfuric acid concentration to by the solid-to-liquid ratio of 1:4 ~ 1:6 be in the 100mL dilute sulphuric acid of 2% (V/V), in 120 DEG C of hydrolysis 120min, filter and use deionized water wash residue to 100mL.Gained filtrate neutralizes pH4.0 ~ 5.0 with calcium hydroxide, and again filter and use deionized water wash residue to 100mL, gained filtrate is the dilute acid hydrolysis liquid of these dregs of a decoction, measures total reducing sugars, glucose, single phenol and polyphenol content wherein, as shown in table 2.
Table 2 different solid is than lower hydrolysis Chinese medicine slag
Embodiment 3:
Take and dry and be crushed to 30 ~ 40 order pulverous tonic semifluid extract of ten ingredients dregs of a decoction 20g to add sulfuric acid concentration to be in the dilute sulphuric acid 100mL of 2% (V/V) (solid-to-liquid ratio 1:5), be hydrolyzed 90 ~ 150min respectively in 120 DEG C, filter and use deionized water wash residue to 100mL.Gained filtrate neutralizes pH4.0 ~ 5.0 with calcium hydroxide, and again filter and use deionized water wash residue to 100mL, gained filtrate is the dilute acid hydrolysis liquid of these dregs of a decoction, measures total reducing sugars, glucose, single phenol and polyphenol content wherein, as shown in table 3.
Chinese medicine slag is hydrolyzed under table 3 different time
Embodiment 4:
The preparation of dilute acid hydrolysis liquid: take and dry and be crushed to 30 ~ 40 order pulverous tonic semifluid extract of ten ingredients dregs of a decoction 200g to add 1000mL concentration to be in the dilute sulphuric acid of 2% (V/V) (solid-to-liquid ratio 1:5), in 120 DEG C of hydrolysis 120min, filter and use deionized water wash residue to 1000mL.Gained filtrate neutralizes pH 4.47 with calcium hydroxide, and again filter and use deionized water wash residue to 1000mL, gained filtrate is the dilute acid hydrolysis liquid of these dregs of a decoction, and recording total reducing sugars is 60.06g/L, and wherein glucose is 36g/L.
Preparation concentration of reduced sugar is 20-60g/L Chinese medicine slag hydrolysate fermentation culture medium, wherein FeSO
47H
2the concentration of O is 0.01g/L, ammonium acetate 2.2g/L, inoculates, passes into sterile nitrogen 5min, in 35 DEG C of anaerobically fermenting 72h, do not regulate and control pH by 10% (V/V) inoculum size.Fermentation results is as shown in table 4.
Table 4 different concns reducing sugar fermentation is for organic solvent
Embodiment 5:
The preparation of dilute acid hydrolysis liquid: take and dry and be crushed to 30 ~ 40 order pulverous tonic semifluid extract of ten ingredients dregs of a decoction 200g to add 800mL concentration to be in the dilute sulphuric acid of 3% (V/V) (solid-to-liquid ratio 1:4), in 115 DEG C of hydrolysis 90min, filter and use deionized water wash residue to 800mL.Gained filtrate neutralizes pH 5.5 with calcium hydroxide, again filters and uses deionized water wash residue to 800mL, and gained filtrate is this dregs of a decoction dilute acid hydrolysis liquid, and recording total reducing sugars is 62.5g/L, and wherein glucose is 39.5g/L.Dregs of a decoction dilute acid hydrolysis liquid is concentrated into 120g/L, and to be mixed with concentration of reduced sugar be 60g/L Chinese medicine slag hydrolysate fermentation culture medium, wherein FeSO
47H
2the concentration of O is 0.01g/L, ammonium acetate 2g/L, and inoculating by 10% (V/V) inoculum size, pass into sterile nitrogen 5min, is 5.5 in 35 DEG C of anaerobically fermenting 72h, Regulation in all life process pH.Consume reducing sugar 54g/L altogether, producing total solvent 21g/L, is 0.39g/g to sugared yield, wherein butanols 13.4g/L, hydrogen producing 4467mL/L.
Embodiment 6:
In the present embodiment, the preparation of Chinese medicine slag dilute acid hydrolysis liquid is identical with embodiment 5, the FeSO in fermention medium
47H
2the addition of O is respectively 0.01-0.50g/L, total reducing sugars concentration 58g/L, and inoculating by 10% (V/V) inoculum size, pass into sterile nitrogen 5min, is 5.5 in 35 DEG C of anaerobically fermenting 72h, Regulation in all life process pH.The fermentation results of gained is as shown in table 5:
Organic solvent fermentation results under the different ferrous sulfate addition of table 5
Claims (10)
1. utilize a method for Chinese medicine slag coproduction organic solvent and hydrogen, it is characterized in that, it comprises the following steps:
(1) collection of Chinese medicine slag and pre-treatment: after Chinese medicine slag is collected, dry and pulverize to obtain Chinese medicine slag powder;
(2) preparation of Chinese medicine slag dilute acid hydrolysis liquid glucose: add dilute sulphuric acid in Chinese medicine slag powder, carries out pyrohydrolysis, and after hydrolysis, filtration residue obtains filtrate; Add calcium hydroxide neutralization filtrate, again cross and filter calcium sulfate precipitation, obtain Chinese medicine slag dilute acid hydrolysis liquid;
(3) preparation of Chinese medicine slag dilute acid hydrolysis liquid fermention medium: with water, FeSO
47H
2o and ammonium acetate preparation substratum, for subsequent use after sterilizing; PH value to 6.5 ~ 7.0 of the Chinese medicine slag dilute acid hydrolysis liquid that regulating step (2) obtains, add substratum after sterilizing, are mixed with the fermention medium that total reducing sugars concentration is 30 ~ 60g/L;
(4) Chinese medicine slag dilute acid hydrolysis liquid fermentation: by inoculum size 10%V/V the inoculation in advance fermention medium of cultured bacterial classification after sterilizing, in 35 DEG C of anaerobically fermenting 48 ~ 72h.
2. the method utilizing Chinese medicine slag coproduction organic solvent and hydrogen according to claim 1, is characterized in that, in step (1), described Chinese medicine slag is the pharmacy residue of Chinese patent medicine tonic semifluid extract of ten ingredients.
3. the method utilizing Chinese medicine slag coproduction organic solvent and hydrogen according to claim 1 and 2, is characterized in that, in step (1), described Chinese medicine slag powder diameter is 30 ~ 40 orders.
4. the method utilizing Chinese medicine slag coproduction organic solvent and hydrogen according to claim 1, it is characterized in that, in step (2), described dilute sulphuric acid is the dilute sulphuric acid of concentration 1 ~ 3%V/V, the mass volume ratio of Chinese medicine slag powder and dilute sulphuric acid is 1g:4 ~ 6mL, and described pyrohydrolysis is be hydrolyzed 90 ~ 150min under 115 ~ 120 DEG C of temperature condition.
5. the method utilizing Chinese medicine slag coproduction organic solvent and hydrogen according to claim 1, is characterized in that, in step (2), adopts the condition of calcium hydroxide neutralization filtrate to be stir at 50 DEG C and add calcium hydroxide, be adjusted to pH4 ~ 6.
6. the method utilizing Chinese medicine slag coproduction organic solvent and hydrogen according to claim 1, is characterized in that, in step (2), the Chinese medicine slag dilute acid hydrolysis liquid obtained, wherein, total reducing sugars concentration is 39 ~ 70g/L, and glucose content is 21 ~ 39g/L.
7. the method utilizing Chinese medicine slag coproduction organic solvent and hydrogen according to claim 1, it is characterized in that, in step (2), obtain Chinese medicine slag dilute acid hydrolysis liquid through concentration, being concentrated into total reducing sugars concentration is 100 ~ 120g/L, then carries out the program of step (3).
8. the method utilizing Chinese medicine slag coproduction organic solvent and hydrogen according to claim 1, is characterized in that, in step (3), adds in the substratum of Chinese medicine slag dilute acid hydrolysis liquid, FeSO
47H
2the concentration of O is 0.01 ~ 0.5g/L, and the concentration of ammonium acetate is 2 ~ 3g/L.
9. the method utilizing Chinese medicine slag coproduction organic solvent and hydrogen according to claim 1, is characterized in that, in step (3), uses the NaOH aqueous solution or the HCl aqueous solution to regulate pH value to 6.5 ~ 7.0 of Chinese medicine slag dilute acid hydrolysis liquid.
10. the method utilizing Chinese medicine slag coproduction organic solvent and hydrogen according to claim 1, is characterized in that, in step (4), described bacterial classification is Bai Shi clostridium Clostridium beijerinckii IB4CCTCC M 2010310.
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