CN101676394B - Method for preparing alcohol by utilizing potato materials - Google Patents
Method for preparing alcohol by utilizing potato materials Download PDFInfo
- Publication number
- CN101676394B CN101676394B CN200810222820XA CN200810222820A CN101676394B CN 101676394 B CN101676394 B CN 101676394B CN 200810222820X A CN200810222820X A CN 200810222820XA CN 200810222820 A CN200810222820 A CN 200810222820A CN 101676394 B CN101676394 B CN 101676394B
- Authority
- CN
- China
- Prior art keywords
- weight
- raw material
- water soluble
- waste liquid
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 224
- 238000000034 method Methods 0.000 title claims abstract description 77
- 244000061456 Solanum tuberosum Species 0.000 title claims abstract description 61
- 235000002595 Solanum tuberosum Nutrition 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 121
- 102000004190 Enzymes Human genes 0.000 claims abstract description 37
- 108090000790 Enzymes Proteins 0.000 claims abstract description 37
- 238000000855 fermentation Methods 0.000 claims abstract description 34
- 230000004151 fermentation Effects 0.000 claims abstract description 34
- 238000000926 separation method Methods 0.000 claims abstract description 33
- 239000000047 product Substances 0.000 claims description 120
- 240000003183 Manihot esculenta Species 0.000 claims description 81
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 80
- 239000002994 raw material Substances 0.000 claims description 80
- 239000002699 waste material Substances 0.000 claims description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 71
- 238000010298 pulverizing process Methods 0.000 claims description 43
- 238000001914 filtration Methods 0.000 claims description 41
- 239000012265 solid product Substances 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 18
- HDSBZMRLPLPFLQ-UHFFFAOYSA-N Propylene glycol alginate Chemical compound OC1C(O)C(OC)OC(C(O)=O)C1OC1C(O)C(O)C(C)C(C(=O)OCC(C)O)O1 HDSBZMRLPLPFLQ-UHFFFAOYSA-N 0.000 claims description 10
- 235000010409 propane-1,2-diol alginate Nutrition 0.000 claims description 10
- 239000000770 propane-1,2-diol alginate Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 9
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 6
- 235000010407 ammonium alginate Nutrition 0.000 claims description 6
- 239000000728 ammonium alginate Substances 0.000 claims description 6
- KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 claims description 6
- 235000010413 sodium alginate Nutrition 0.000 claims description 6
- 239000000661 sodium alginate Substances 0.000 claims description 6
- 229940005550 sodium alginate Drugs 0.000 claims description 6
- 235000010408 potassium alginate Nutrition 0.000 claims description 5
- 239000000737 potassium alginate Substances 0.000 claims description 5
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 claims description 5
- 108010028688 Isoamylase Proteins 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 108010019077 beta-Amylase Proteins 0.000 claims description 3
- 239000002054 inoculum Substances 0.000 claims description 2
- 241000195493 Cryptophyta Species 0.000 claims 14
- 150000002148 esters Chemical class 0.000 claims 7
- 230000002478 diastatic effect Effects 0.000 claims 1
- 235000010443 alginic acid Nutrition 0.000 abstract description 57
- 229920000615 alginic acid Polymers 0.000 abstract description 57
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical class O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 abstract description 55
- 238000002156 mixing Methods 0.000 abstract description 6
- 239000010808 liquid waste Substances 0.000 abstract 4
- 229940072056 alginate Drugs 0.000 description 54
- 239000002245 particle Substances 0.000 description 33
- 229940088598 enzyme Drugs 0.000 description 32
- 229920002472 Starch Polymers 0.000 description 30
- 235000019698 starch Nutrition 0.000 description 30
- 239000008107 starch Substances 0.000 description 30
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 26
- 235000014680 Saccharomyces cerevisiae Nutrition 0.000 description 26
- 238000001035 drying Methods 0.000 description 20
- 239000007787 solid Substances 0.000 description 19
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 16
- 229960001031 glucose Drugs 0.000 description 16
- 239000008103 glucose Substances 0.000 description 16
- 239000012528 membrane Substances 0.000 description 13
- 241001474374 Blennius Species 0.000 description 12
- 239000006228 supernatant Substances 0.000 description 12
- 239000002609 medium Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 108010065511 Amylases Proteins 0.000 description 9
- 102000013142 Amylases Human genes 0.000 description 9
- 235000019418 amylase Nutrition 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000007071 enzymatic hydrolysis Effects 0.000 description 8
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 8
- 244000005700 microbiome Species 0.000 description 8
- 238000003825 pressing Methods 0.000 description 8
- 239000004382 Amylase Substances 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 6
- 230000001332 colony forming effect Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005374 membrane filtration Methods 0.000 description 5
- 239000010812 mixed waste Substances 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 241000235527 Rhizopus Species 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 229920001542 oligosaccharide Polymers 0.000 description 4
- 150000002482 oligosaccharides Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- 229920000945 Amylopectin Polymers 0.000 description 3
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 108090000637 alpha-Amylases Proteins 0.000 description 3
- 102000004139 alpha-Amylases Human genes 0.000 description 3
- 229940024171 alpha-amylase Drugs 0.000 description 3
- 239000001963 growth medium Substances 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 229920000856 Amylose Polymers 0.000 description 2
- 241000228212 Aspergillus Species 0.000 description 2
- 241000228245 Aspergillus niger Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 108010073178 Glucan 1,4-alpha-Glucosidase Proteins 0.000 description 2
- 102100022624 Glucoamylase Human genes 0.000 description 2
- 244000017020 Ipomoea batatas Species 0.000 description 2
- 235000002678 Ipomoea batatas Nutrition 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 2
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229940025131 amylases Drugs 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000011534 incubation Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 235000012015 potatoes Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 239000008223 sterile water Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 102000003925 1,4-alpha-Glucan Branching Enzyme Human genes 0.000 description 1
- 108090000344 1,4-alpha-Glucan Branching Enzyme Proteins 0.000 description 1
- 241001513093 Aspergillus awamori Species 0.000 description 1
- 240000006439 Aspergillus oryzae Species 0.000 description 1
- 235000002247 Aspergillus oryzae Nutrition 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 101001052076 Homo sapiens Maltase-glucoamylase Proteins 0.000 description 1
- 102100024295 Maltase-glucoamylase Human genes 0.000 description 1
- 235000004456 Manihot esculenta Nutrition 0.000 description 1
- 244000149260 Manihot esculenta subsp flabellifolia Species 0.000 description 1
- 241000228347 Monascus <ascomycete fungus> Species 0.000 description 1
- 102000045595 Phosphoprotein Phosphatases Human genes 0.000 description 1
- 108700019535 Phosphoprotein Phosphatases Proteins 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 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 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229940077731 carbohydrate nutrients Drugs 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000007430 reference method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000003248 secreting effect Effects 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
- Y02P60/87—Re-use of by-products of food processing for fodder production
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
Description
技术领域 technical field
本发明是关于乙醇的制备方法,更具体地是关于采用薯类原料制备乙醇的方法。The invention relates to a method for preparing ethanol, more particularly to a method for preparing ethanol by using tuber raw materials.
背景技术 Background technique
薯类,例如红薯、马铃薯、木薯等,富含淀粉,因此广泛用于发酵制糖、制淀粉等领域。Potatoes, such as sweet potatoes, potatoes, cassava, etc., are rich in starch, so they are widely used in the fields of fermentation sugar and starch production.
木薯是热带和亚热带多年生、温带一年生薯属灌木,原产于南美洲,适宜在平均温度为25-29℃、年均降水量1000-1500毫米的低纬度地区生长。大约在1820年前,木薯传到中国南方,主要在广东、广西和海南种植,现在逐渐扩大到云南、福建、贵州等省。木薯分为两类:苦味木薯(有毒木薯)和甜味木薯(无毒木薯)。新鲜的木薯块根的主要化学成分是水,其次是碳水化合物,还有一些含量较少的蛋白质、脂肪和果胶。鲜木薯淀粉含量达到25-30重量%,干木薯淀粉含量为70重量%左右。Cassava is a tropical and subtropical perennial and temperate annual tuber shrub. It is native to South America and is suitable for growth in low latitude areas with an average temperature of 25-29°C and an average annual precipitation of 1000-1500 mm. About 1820 years ago, cassava spread to southern China and was mainly grown in Guangdong, Guangxi and Hainan, and now gradually expanded to Yunnan, Fujian, Guizhou and other provinces. There are two types of cassava: bitter cassava (poisonous cassava) and sweet cassava (non-toxic cassava). The main chemical composition of fresh cassava root is water, followed by carbohydrates, and some lesser amounts of protein, fat and pectin. The content of fresh cassava starch reaches 25-30% by weight, and the content of dry cassava starch is about 70% by weight.
由于薯类原料发酵制备乙醇的废液含有高浓度的有机物,目前绝大部分乙醇厂排放的薯类原料发酵制备乙醇的废液没有经过有效处理直接向外排放,对当地和下游的水环境造成严重影响。Since the waste liquid produced by fermenting potato raw materials to ethanol contains high concentrations of organic matter, the waste liquid discharged from most ethanol plants by fermenting potato raw materials to produce ethanol is directly discharged outside without effective treatment, causing damage to the local and downstream water environment. Serious impact.
目前,薯类原料发酵制备乙醇的废液的处理方法有:1、焚烧法,即将薯类原料发酵制备乙醇的废液浓缩后进行焚烧,该方法的缺点为焚烧后容易造成二次污染;2、用薯类原料发酵制备乙醇的废液发酵制备沼气,该方法的缺点为投资大和控制技术要求高。At present, the treatment methods for the waste liquid produced by fermentation of potato raw materials to produce ethanol include: 1. Incineration method, that is, the waste liquid produced by fermentation of potato raw materials to produce ethanol is concentrated and then incinerated. The disadvantage of this method is that it is easy to cause secondary pollution after incineration; 2. 1. Fermentation of waste liquid from potato raw materials to produce ethanol to produce biogas. The disadvantages of this method are large investment and high control technology requirements.
因此,目前通常采用回收木薯发酵制备乙醇的废液中的固体残渣作为饲料来处理废液的方法,该方法包括将废液进行固液分离,得到固体产物;之后对固体产物进行烘干。该方法是一种投资少、容易操作并且对环境友好的木薯发酵制备乙醇的废液的处理方法。在这种情况下,固液分离的处理能力就成为决定废液处理能力大小的关键因素。Therefore, at present, the solid residue in the waste liquid produced by cassava fermentation to produce ethanol is usually used as feed to process the waste liquid. The method includes separating the waste liquid from solid to liquid to obtain a solid product; and then drying the solid product. The method is a treatment method for the waste liquid produced by cassava fermentation to produce ethanol with low investment, easy operation and environmental friendliness. In this case, the processing capacity of solid-liquid separation becomes a key factor in determining the size of waste liquid processing capacity.
目前对木薯发酵制备乙醇的废液进行处理的方法存在的问题是,固液分离的周期过长,导致废液的处理量小,并导致木薯发酵制备乙醇的装置的运行负荷较低,生产能力不能够达到要求。The problem with the current method for treating the waste liquid produced by cassava fermentation to ethanol is that the period of solid-liquid separation is too long, resulting in a small amount of waste liquid treatment, and the lower operating load of the device for producing ethanol by cassava fermentation. Unable to meet the requirements.
发明内容 Contents of the invention
本发明的目的是克服现有的采用薯类原料制备乙醇的方法存在固液分离的周期过长的缺点,提供一种固液分离的周期较短的采用薯类原料制备乙醇的方法。The purpose of the present invention is to overcome the shortcoming of too long period of solid-liquid separation in the existing method for preparing ethanol from potato raw materials, and provide a method for preparing ethanol from potato raw materials with a shorter period of solid-liquid separation.
本发明提供了一种采用薯类原料制备乙醇的方法,该方法包括将薯类原料粉碎,将粉碎后的产物与酶混合、酶解,得到酶解产物;发酵该酶解产物,从发酵产物中分离乙醇,然后对废液进行固液分离,其中,在对废液进行固液分离之前在废液中加入水溶性海藻酸酯和/或水溶性海藻酸盐。The invention provides a method for preparing ethanol from potato raw materials. The method comprises pulverizing the potato raw materials, mixing the pulverized products with enzymes, and enzymatically hydrolyzing them to obtain enzymatic hydrolysis products; Separating ethanol from the waste liquid, and then carrying out solid-liquid separation on the waste liquid, wherein, adding water-soluble alginate and/or water-soluble alginate to the waste liquid before carrying out solid-liquid separation on the waste liquid.
本发明中,通过在木薯发酵制备乙醇的废液中加入水溶性海藻酸酯和/或水溶性海藻酸盐,显著地缩短了固液分离的时间,在无需增加新设备的情况下显著地提高了单位时间内废液的处理量,从而解决了导致木薯发酵制备乙醇的装置的运行负荷较低的瓶颈,提高了木薯发酵制备乙醇的装置的生产能力。In the present invention, by adding water-soluble alginate and/or water-soluble alginate to the waste liquid of cassava fermentation to prepare ethanol, the time of solid-liquid separation is significantly shortened, and the time for solid-liquid separation is significantly improved without adding new equipment. The processing capacity of the waste liquid per unit time is reduced, thereby solving the bottleneck of the lower operating load of the device for producing ethanol by cassava fermentation, and improving the production capacity of the device for producing ethanol by cassava fermentation.
具体实施方式 Detailed ways
本发明提供了一种采用薯类原料制备乙醇的方法,该方法包括将薯类原料粉碎,将粉碎后的产物与酶混合、酶解,得到酶解产物;发酵该酶解产物,从发酵产物中分离乙醇,然后对废液进行固液分离,其中,在对废液进行固液分离之前在废液中加入水溶性海藻酸酯和/或水溶性海藻酸盐。The invention provides a method for preparing ethanol from potato raw materials. The method comprises pulverizing the potato raw materials, mixing the pulverized products with enzymes, and enzymatically hydrolyzing them to obtain enzymatic hydrolysis products; Separating ethanol from the waste liquid, and then carrying out solid-liquid separation on the waste liquid, wherein, adding water-soluble alginate and/or water-soluble alginate to the waste liquid before carrying out solid-liquid separation on the waste liquid.
根据本发明,水溶性海藻酸酯和/或水溶性海藻酸盐的用量可以在很大范围内改变,只要能够缩短了固液分离的时间即可,优选情况下,相对于1000重量份的废液,水溶性海藻酸酯和/或水溶性海藻酸盐的用量为0.05-1重量份;进一步优选为,相对于1000重量份的废液,水溶性海藻酸酯和/或水溶性海藻酸盐的用量为0.1-0.5重量份。According to the present invention, the amount of water-soluble alginate and/or water-soluble alginate can be changed in a wide range, as long as the time of solid-liquid separation can be shortened, preferably, relative to 1000 parts by weight of waste Liquid, the consumption of water-soluble alginate and/or water-soluble alginate is 0.05-1 weight part; The consumption is 0.1-0.5 weight part.
所述水溶性海藻酸盐的种类可以在很大范围内改变,只要能够使废液中分子间的碰撞加剧,使不易沉淀的小分子结合成为大分子形成较大的絮凝物即可,优选情况下,所述水溶性海藻酸盐的相对分子量为30000-200000,相对分子量为物质的分子或特定单元的平均质量与核素12C原子质量的1/12之比。例如,所述水溶性海藻酸盐可以选自海藻酸钠、海藻酸钾和海藻酸铵中的一种或几种。符合上述要求的水溶性海藻酸盐可以通过商购得到,例如,青岛南洋海藻工业有限公司生产的海藻酸钠、青岛明月海藻集团有限公司生产的海藻酸钾以及邯郸市海洋药用海藻制品有限公司生产的海藻酸铵。The type of water-soluble alginate can be changed in a wide range, as long as the collision between molecules in the waste liquid can be intensified, and the small molecules that are not easy to precipitate can be combined into macromolecules to form larger flocs. Here, the relative molecular weight of the water-soluble alginate is 30,000-200,000, and the relative molecular weight is the ratio of the average mass of a molecule or a specific unit of a substance to 1/12 of the atomic mass of nuclide 12 C. For example, the water-soluble alginate may be selected from one or more of sodium alginate, potassium alginate and ammonium alginate. Water-soluble alginates that meet the above requirements can be obtained commercially, for example, sodium alginate produced by Qingdao Nanyang Seaweed Industry Co., Ltd., potassium alginate produced by Qingdao Mingyue Seaweed Group Co., Ltd., and Handan Ocean Medicinal Seaweed Products Co., Ltd. Production of ammonium alginate.
所述水溶性海藻酸酯的种类可以在很大范围内改变,只要能够使废液中分子间的碰撞加剧,使不易沉淀的小分子结合成为大分子形成较大的絮凝物即可,优选情况下,所述水溶性海藻酸酯的相对分子量为30000-200000,相对分子量为物质的分子或特定单元的平均质量与核素12C原子质量的1/12之比。例如,所述水溶性海藻酸酯可以选自海藻酸丙二醇酯、海藻酸乙二醇酯和海藻酸丁二醇酯中的一种或几种,优选为海藻酸丙二醇酯。符合上述要求的水溶性海藻酸酯可以通过本领域技术人员公知的方法合成得到,也可以通过商购得到,例如,青岛明月海藻集团有限公司生产的海藻酸丙二醇酯。The type of water-soluble alginate can be changed in a wide range, as long as the collision between molecules in the waste liquid can be intensified, and the small molecules that are not easy to precipitate can be combined into macromolecules to form larger flocs. Here, the relative molecular weight of the water-soluble alginate is 30,000-200,000, and the relative molecular weight is the ratio of the average mass of a molecule or a specific unit of a substance to 1/12 of the atomic mass of nuclide 12 C. For example, the water-soluble alginate may be selected from one or more of propylene glycol alginate, ethylene glycol alginate and butylene glycol alginate, preferably propylene glycol alginate. Water-soluble alginate that meets the above requirements can be synthesized by methods known to those skilled in the art, or can be obtained commercially, for example, propylene glycol alginate produced by Qingdao Mingyue Seaweed Group Co., Ltd.
优选情况下,在对废液进行固液分离之前在废液中加入水溶性海藻酸酯和水溶性海藻酸盐,在同时加入水溶性海藻酸酯和水溶性海藻酸盐时,能够进一步缩短固液分离的时间,从而进一步提高单位时间内废液的处理量。在这种情况下,水溶性海藻酸酯和水溶性海藻酸盐的用量可以在很大范围内改变,优选情况下,相对于100重量份的水溶性海藻酸酯,所述水溶性海藻酸盐的加入量为10-1000重量份。进一步优选为,相对于100重量份的水溶性海藻酸酯,所述水溶性海藻酸盐的加入量为40-300重量份。Preferably, water-soluble alginate and water-soluble alginate are added to the waste liquid before solid-liquid separation is carried out, and when adding water-soluble alginate and water-soluble alginate at the same time, the solid The time of liquid separation can further increase the treatment capacity of waste liquid per unit time. In this case, the amount of water-soluble alginate and water-soluble alginate can be changed in a wide range, preferably, with respect to 100 parts by weight of water-soluble alginate, the water-soluble alginate The addition amount of is 10-1000 parts by weight. Further preferably, relative to 100 parts by weight of the water-soluble alginate, the added amount of the water-soluble alginate is 40-300 parts by weight.
按照本发明,将薯类原料粉碎的方法可以为能够用于粉碎薯类原料粉碎的各种方法,例如,所述木薯的粉碎方法可以包括将木薯与水混合后进行粉碎,但该方法得到的粉碎的薯类原料的粒径较大且不均匀,从而导致后续的乙醇产率较低而残糖率较高,因此,优选情况下,所述粉碎的方法包括先将薯类原料进行一次粉碎,得到一次粉碎产物,将部分一次粉碎产物进行二次粉碎,得到二次粉碎产物,将剩余部分的一次粉碎产物与未粉碎的薯类原料混合然后进行一次粉碎;在对废液进行固液分离之前在废液中加入水溶性海藻酸酯和/或水溶性海藻酸盐。According to the present invention, the method for pulverizing potato raw materials can be various methods that can be used for pulverizing potato raw materials. For example, the pulverizing method of cassava may include mixing cassava with water and then pulverizing, but the method obtained The particle size of the pulverized potato raw material is relatively large and uneven, resulting in a lower yield of ethanol and a higher residual sugar rate. Therefore, preferably, the pulverizing method includes first pulverizing the potato raw material once , to obtain a primary pulverization product, and carry out secondary pulverization on part of the primary pulverization product to obtain a secondary pulverization product, mix the remaining part of the primary pulverization product with uncrushed potato raw materials and then perform primary pulverization; after solid-liquid separation of the waste liquid Water-soluble alginate and/or water-soluble alginate were previously added to the waste liquid.
按照本发明,所述剩余部分的一次粉碎产物为全部一次粉碎产物重量的5-20重量%;剩余部分的一次粉碎产物占剩余部分的一次粉碎产物与未粉碎的薯类原料的总重量的5-20重量%。优选情况下,所述剩余部分的一次粉碎产物为全部一次粉碎产物重量的5-10重量%;剩余部分的一次粉碎产物占剩余部分的一次粉碎产物与未粉碎的薯类原料的总重量的5-10重量%。按照本发明的方法粉碎得到的最终粉碎产物中薯类原料颗粒的粒度小且颗粒粒度分布更均匀,该薯类原料的平均颗粒直径可以达到1.8至小于2.5毫米,甚至更小,如优选为1.6至小于1.8毫米。According to the present invention, the primary crushed product of the remaining part is 5-20% by weight of the total primary crushed product; -20% by weight. Preferably, the primary crushed product of the remaining part is 5-10% by weight of the total primary crushed product weight; the primary crushed product of the remaining part accounts for 5% of the total weight of the primary crushed product of the remaining part and the unpulverized tuber raw material. -10% by weight. The particle size of the potato raw material particles in the final pulverized product obtained by pulverizing according to the method of the present invention is small and the particle size distribution is more uniform. The average particle diameter of the potato raw material can reach 1.8 to less than 2.5 mm, or even smaller, such as preferably 1.6 mm. to less than 1.8 mm.
根据本发明提供的方法,在将薯类原料进行一次粉碎前,无需将薯类原料与水混合,或者仅仅加入少量的水,例如,所述水的用量可以为薯类原料干重的0.5-2倍,优选为1-1.5倍。优选情况下,在粉碎薯类原料之前无需特别将薯类原料与水混合,而是在将一次粉碎后的部分一次粉碎产物返回与未经过粉碎的薯类原料重新混合,然后进行一次粉碎,该返回的部分一次粉碎产物为薯类原料颗粒的淀粉浆液,该返回部分的一次粉碎产物既能够起到稀释的作用,因此在初始粉碎时可以不将薯类原料与水混合,此外,该返回部分的一次粉碎产物又能够与鲜木薯原料一起被再次粉碎,不但消耗水的量少,消耗的能量较少,设备的利用率高,粉碎效果高,且本发明的二次粉碎的方法能够很好的控制粉碎后的得到的粉碎产物中薯类原料颗粒的粒径,使最终得到的薯类原料颗粒的粒径小且均匀。按照本发明,为了使最终得到的粉碎产物中薯类原料颗粒的直径在1.8至小于2.5毫米,优选为1.6至小于1.8毫米,在将薯类原料进行一次粉碎后,得到的一次粉碎产物中薯类原料的平均颗粒直径一般在2.5-10毫米,优选为2.5-5毫米。According to the method provided by the present invention, before the potato raw material is crushed once, it is not necessary to mix the potato raw material with water, or only a small amount of water is added, for example, the amount of water can be 0.5-5% of the dry weight of the potato raw material. 2 times, preferably 1-1.5 times. Preferably, it is not necessary to mix the potato raw material with water before pulverizing the potato raw material. Instead, the part of the primary crushed product after the primary pulverization is returned to be remixed with the potato raw material that has not been pulverized, and then the primary pulverization is performed. The returned part of the primary crushed product is the starch slurry of potato raw material granules. The primary crushed product of this returned part can play a role of dilution, so the potato raw material can not be mixed with water during the initial crushing. In addition, the returned part The primary crushed product can be crushed again together with fresh cassava raw materials, not only consumes less water, consumes less energy, has high utilization rate of equipment, high crushing effect, and the secondary crushing method of the present invention can be very good Controlling the particle size of potato raw material particles in the pulverized product obtained after crushing, so that the particle size of the finally obtained potato raw material particles is small and uniform. According to the present invention, in order to make the diameter of the potato raw material particles in the finally obtained crushed product be 1.8 to less than 2.5 mm, preferably 1.6 to less than 1.8 mm, after primary crushing of the potato raw material, the obtained primary crushed product of potato The average particle diameter of the quasi-raw material is generally 2.5-10 mm, preferably 2.5-5 mm.
根据本发明的一个具体实施方式,当所述进料方式为连续进料时,可以将剩余部分的一次粉碎产物与未粉碎的薯类原料混合并进行一次粉碎后的一次粉碎产物中的部分取出,继续与未经过粉碎的薯类原料混合并进行一次粉碎,并按照这样的方法循环、连续的进行粉碎。According to a specific embodiment of the present invention, when the feeding method is continuous feeding, the remaining part of the primary crushed product can be mixed with the uncrushed tuber raw material and the part of the primary crushed product after primary crushing can be taken out , continue to mix with the potato raw materials that have not been crushed and perform primary crushing, and perform circular and continuous crushing according to this method.
根据本发明的另一个具体实施方式,当所述进料方式为间歇进料时,可以将剩余部分的一次粉碎产物与未经过粉碎的薯类原料混合并进行一次粉碎后得到的一次粉碎产物直接进行二次粉碎得到二次粉碎产物,也可以将该一次粉碎产物与初次粉碎后的得到的一次粉碎产物混合后一起进行二次粉碎。According to another specific embodiment of the present invention, when the feeding method is intermittent feeding, the remaining part of the primary pulverization product can be mixed with the raw potato raw materials that have not been pulverized and the primary pulverization product obtained after primary pulverization can be directly Secondary pulverization is performed to obtain a secondary pulverization product, and the primary pulverization product may be mixed with the primary pulverization product obtained after the primary pulverization to perform secondary pulverization together.
可以使用常规的各种粉碎设备,例如SFSP系列锤片式粉碎机。Conventional various crushing equipment can be used, such as SFSP series hammer mills.
所述薯类原料可以为各种薯类原料,如红薯、马铃薯、木薯等,本发明的具体实施方案中采用的薯类原料为木薯。所述木薯可以为鲜木薯或干木薯,也可以为鲜木薯与干木薯的混合物。所述干木薯与鲜木薯的重量没有特别限定,通常情况下,所述干木薯与鲜木薯的重量比为1:1.5-2.5,优选为1:1.5-2。The potato raw material can be various potato raw materials, such as sweet potato, potato, cassava, etc. The potato raw material adopted in the specific embodiment of the present invention is cassava. The cassava can be fresh cassava or dry cassava, or a mixture of fresh cassava and dry cassava. The weight of the dry cassava and the fresh cassava is not particularly limited. Usually, the weight ratio of the dry cassava to the fresh cassava is 1:1.5-2.5, preferably 1:1.5-2.
成熟的木薯一般粗4-8厘米,长20-30厘米,薯形粗短,呈短圆柱状,木薯由内及外的机构为薯肉,内表皮和外表皮,外表皮为深褐色,间有白色环状条纹,内皮和肉质白色。由于薯类原料中可能会含有泥土、沙石杂质以及铁杂质,会对破碎设备造成损害,因此,按照本发明的方法,还可以包括破碎之前对薯类原料进行预处理的常规操作,所述预处理的步骤一般包括除去杂质和清洗的步骤。如,在鲜木薯采收后,除去木薯上的泥土、根、须及木质部分以及砂石等杂质。并对木薯进行清洗,所述清洗的方法和设备为本领域技术人员所公知,在这里不再赘述。Mature cassava is generally 4-8 cm thick and 20-30 cm long. There are white ring-shaped stripes, and the inner bark and flesh are white. Since the potato raw materials may contain soil, sand and stone impurities and iron impurities, which will cause damage to the crushing equipment, therefore, according to the method of the present invention, it may also include the conventional operation of pretreating the potato raw materials before crushing. The steps of pretreatment generally include the steps of removing impurities and cleaning. For example, after the fresh cassava is harvested, impurities such as soil, roots, whiskers, woody parts, and sand and stones on the cassava are removed. And cassava is cleaned, and the method and equipment of described cleaning are known to those skilled in the art, do not repeat them here.
所述酶解步骤可以通过本领域常用的方法完成,比如向粉碎产物中添加产酶微生物和/或酶,在产酶微生物的生长温度和/或酶有活力的温度下保温完成。所述产酶微生物为能够分泌淀粉酶的产酶微生物。所述酶包括淀粉酶。The enzymolysis step can be accomplished by methods commonly used in the art, such as adding enzyme-producing microorganisms and/or enzymes to the pulverized product, and incubating at the growth temperature of the enzyme-producing microorganisms and/or the temperature at which the enzymes are active. The enzyme-producing microorganism is an enzyme-producing microorganism capable of secreting amylase. The enzymes include amylases.
由于微生物生长会产生副产物,因此优选直接加入酶。所述酶的用量越多越好,出于成本考虑,优选以每克粉碎后的产物的干重计,所述淀粉酶的用量为4-50酶活力单位,更优选以每克粉碎后的产物的干重计,所述淀粉酶的用量为10-30酶活力单位。Direct addition of the enzyme is preferred due to by-products produced by microbial growth. The more the amount of the enzyme, the better, for cost considerations, preferably based on the dry weight per gram of the crushed product, the amount of the amylase is 4-50 enzyme activity units, more preferably per gram of the crushed product Based on the dry weight of the product, the amylase is used in an amount of 10-30 enzyme activity units.
本发明所述酶的酶活力单位的定义为:在pH值为6.0、温度为70℃的条件下,1分钟将1毫克淀粉转化为葡萄糖所需的酶量为一个酶活力单位。The enzyme activity unit of the enzyme in the present invention is defined as: under the conditions of pH value 6.0 and temperature 70° C., the amount of enzyme required to convert 1 mg of starch into glucose in 1 minute is an enzyme activity unit.
所述酶解的温度可以为淀粉酶的任何最适作用温度,一般为50-90℃,更优选60-70℃。所述酶解的时间理论上越长越好,考虑到设备利用率,优选所述酶解的时间为20-240分钟,更优选为30-120分钟。所述酶解的pH值可以为淀粉酶的任何最适作用pH,一般为3-7,更优选pH值为5-6。由于酶解过程中pH值的波动不大,因此所述酶解的pH值可以按照本领域常用的方法在加入酶之前进行调节,例如先将粉碎产物与水或培养基(加酶一般与水混合,加入产酶微生物一般与该微生物的培养基)混合,此外,为了保证蒸馏得到的乙醇的浓度,一般使所得混合物的固含量为20-40重量%,根据所得混合物的pH值,用硫酸溶液或氢氧化钠将待酶解的混合物pH调节至3-7,更优选调节至pH值为5-6。The enzymolysis temperature can be any optimum action temperature of amylase, generally 50-90°C, more preferably 60-70°C. Theoretically, the longer the enzymatic hydrolysis time, the better. Considering the equipment utilization rate, the enzymatic hydrolysis time is preferably 20-240 minutes, more preferably 30-120 minutes. The pH value of the enzymatic hydrolysis can be any optimum action pH of amylase, generally 3-7, more preferably 5-6. Because the fluctuation of the pH value in the enzymolysis process is not large, the pH value of the enzymolysis can be adjusted according to the methods commonly used in the art before adding the enzyme, such as first mixing the pulverized product with water or culture medium (enzyme is generally mixed with water) Mixing, adding enzyme-producing microorganisms (generally mixed with the culture medium of the microorganisms), in addition, in order to ensure the concentration of ethanol obtained by distillation, generally the solid content of the resulting mixture is 20-40% by weight, according to the pH value of the resulting mixture, use sulfuric acid solution or sodium hydroxide to adjust the pH of the mixture to be hydrolyzed to 3-7, more preferably to pH 5-6.
淀粉酶是能够分解淀粉糖苷键的一类酶的总称,所述淀粉酶一般包括α-淀粉酶、β-淀粉酶、糖化酶和异淀粉酶。本发明所述酶包括淀粉酶。Amylase is a general term for a class of enzymes capable of decomposing starch glycosidic bonds, and the amylase generally includes α-amylase, β-amylase, glucoamylase and isoamylase. The enzymes of the present invention include amylases.
α-淀粉酶又称淀粉1,4-糊精酶,它能够任意地、不规则地切开淀粉链内部的α-1,4-糖苷键,将淀粉水解为麦芽糖、含有6个葡萄糖单位的寡糖和带有支链的寡糖。生产此酶的微生物主要有枯草杆菌、黑曲霉、米曲霉和根霉。α-amylase, also known as starch 1,4-dextrinase, can arbitrarily and irregularly cut the α-1,4-glucosidic bond inside the starch chain, and hydrolyze starch into maltose, which contains 6 glucose units. Oligosaccharides and branched oligosaccharides. The microorganisms producing this enzyme mainly include Bacillus subtilis, Aspergillus niger, Aspergillus oryzae and Rhizopus.
β-淀粉酶又称淀粉1,4-麦芽糖苷酶,能够从淀粉分子非还原性末端切开1,4-糖苷键,生成麦芽糖。此酶作用于淀粉的产物是麦芽糖与极限糊精。此酶主要由曲霉、根霉和内孢霉产生。β-amylase, also known as starch 1,4-maltosidase, can cut 1,4-glucosidic bonds from the non-reducing ends of starch molecules to generate maltose. The products of this enzyme acting on starch are maltose and limit dextrin. This enzyme is mainly produced by Aspergillus, Rhizopus and Endospora.
糖化酶又称淀粉α-1,4-葡萄糖苷酶,此酶作用于淀粉分子的非还原性末端,以葡萄糖为单位,依次作用于淀粉分子中的α-1,4-糖苷键,生成葡萄糖。此酶作用于支链淀粉后的产物有葡萄糖和带有α-1,6-糖苷键的寡糖;作用于直链淀粉后的产物几乎全部是葡萄糖。此酶产生菌主要是黑曲霉(左美曲霉、泡盛曲霉)、根霉(雪白根酶、德氏根霉)、拟内孢霉、红曲霉。Glucoamylase, also known as starch α-1,4-glucosidase, acts on the non-reducing end of the starch molecule, taking glucose as the unit, and acts on the α-1,4-glucosidic bond in the starch molecule in turn to generate glucose . The products of this enzyme after acting on amylopectin include glucose and oligosaccharides with α-1,6-glycosidic bonds; the products after acting on amylose are almost all glucose. The enzyme-producing bacteria are mainly Aspergillus niger (Aspergillus levomerus, Aspergillus awamori), Rhizopus (Rhizosimus nigeriensis, Rhizopus delbrueckii), Endospora, and Monascus.
异淀粉酶又称淀粉α-1,6-葡萄糖苷酶、分枝酶,此酶作用于枝链淀粉分子分枝点处的α-1,6-糖苷键,将枝链淀粉的整个侧链切下变成直链淀粉。此酶产生菌主要是嫌气杆菌、芽孢杆菌及某些假单孢杆菌等细菌。Isoamylase, also known as starch α-1,6-glucosidase, branching enzyme, this enzyme acts on the α-1,6-glucosidic bond at the branch point of the amylopectin molecule, and the entire side chain of the amylopectin Cut into amylose. The enzyme-producing bacteria are mainly bacteria such as Aerobacter, Bacillus and some Pseudomonas.
优选所述酶解使用的酶还包括磷酸酯酶。因为磷酸酯酶能够使磷酸与醇式羟基结合成酯的磷酸糊精水解成葡萄糖,并释放出磷酸,具有极明显的液化力,所以酶解使用的酶包括磷酸酯酶,可以更充分地水解淀粉,以增加乙醇产率。Preferably, the enzymes used in the enzymolysis also include phosphatases. Because phosphatase can hydrolyze the phosphodextrin formed by the combination of phosphoric acid and alcoholic hydroxyl group into glucose, and release phosphoric acid, which has a very obvious liquefaction power, so the enzymes used in enzymatic hydrolysis include phosphatase, which can hydrolyze more fully starch to increase ethanol yield.
能够发酵单糖如葡萄糖和/或果糖、寡糖如蔗糖和/或半乳糖的微生物都可以用于本发明的发酵过程,由于酿酒酵母是酿酒工业上普遍应用的耐酒精、副产物少、乙醇产率高的发酵己糖的微生物,因此优选所述发酵所使用的酵母为酿酒酵母。Microbes capable of fermenting monosaccharides such as glucose and/or fructose, oligosaccharides such as sucrose and/or galactose can be used in the fermentation process of the present invention, because Saccharomyces cerevisiae is alcohol-resistant, by-product few, ethanol that is generally used in the brewing industry Hexose-fermenting microorganisms with high yields, so it is preferred that the yeast used for the fermentation is Saccharomyces cerevisiae.
以每克酶解产物计,所述发酵所使用的酵母的接种量为103-108菌落形成单位,更优选104-106菌落形成单位。Calculated per gram of enzymatic hydrolysis product, the inoculum amount of yeast used in the fermentation is 10 3 -10 8 colony forming units, more preferably 10 4 -10 6 colony forming units.
所述菌落形成单位的定义为将稀释后的一定量的菌液通过浇注或涂布的方法,让其内的微生物单细胞一一分散在培养基平板上,待培养后,每一活细胞就形成一个菌落。即每毫升菌液中含有的单细胞的数目。The definition of the colony-forming unit is that a certain amount of diluted bacterial solution is poured or coated, and the microbial single cells in it are dispersed on the medium plate one by one. After culturing, each living cell will form a colony. That is, the number of single cells contained in each milliliter of bacterial liquid.
本发明发酵所使用的酵母可以为商购酵母固体制剂(比如干酵母粉)或酵母菌种,比如拉斯2号(Rasse II)酵母,又名德国二号酵母、拉斯12号(Rasse XII)酵母,又名德国12号酵母、K字酵母、南阳五号酵母(1300)和南阳混合酵母(1308)。所述酵母的菌落形成单位可以通过本领域公知的方法测定,比如亚甲基蓝染色活菌计数法。亚甲基蓝染色活菌计数法的具体方法如下:The yeast used for the fermentation of the present invention can be commercially available yeast solid preparations (such as dry yeast powder) or yeast strains, such as Lars No. 2 (Rasse II) yeast, also known as German No. 2 yeast, Rass No. 12 (Rasse XII) ) yeast, also known as German No. 12 yeast, K word yeast, Nanyang No. 5 yeast (1300) and Nanyang mixed yeast (1308). The colony forming unit of the yeast can be determined by methods known in the art, such as methylene blue staining viable count method. The specific method of methylene blue staining viable count method is as follows:
将1克干酵母粉溶于10毫升无菌水中,或将1毫升菌种活化液用无菌水稀释至10毫升,加入0.5毫升0.1重量%亚甲基蓝,在35℃下保温30分钟。在10倍光学显微镜下,用血球计数板计数保温后的溶液中活菌的数目(死菌染色,活菌不染色),可得1克干酵母或1毫升菌种活化液中活菌的数目,即菌落形成单位数。Dissolve 1 gram of dry yeast powder in 10 milliliters of sterile water, or dilute 1 milliliter of strain activation solution with sterile water to 10 milliliters, add 0.5 milliliters of 0.1 wt% methylene blue, and incubate at 35° C. for 30 minutes. Under a 10x optical microscope, use a hemocytometer to count the number of viable bacteria in the solution after incubation (dead bacteria are stained, live bacteria are not stained), and the number of viable bacteria in 1 gram of dry yeast or 1 ml of strain activation solution can be obtained , the number of colony-forming units.
所述酵母可以采用常规的方法接种,例如向酶解产物中加入5-15体积%的种子液。所述种子液可以为干酵母的水溶液或培养基溶液,也可以为干酵母或商购菌种的活化种子液。The yeast can be inoculated by a conventional method, for example, adding 5-15 volume % seed liquid to the enzymatic hydrolysis product. The seed solution may be an aqueous solution or a culture medium solution of dry yeast, or may be an activated seed solution of dry yeast or commercially available strains.
所述发酵的温度可以为任何适于酵母生长的温度,优选为30-36℃,更优选为30-33℃。pH值为4-6,优选为4-4.5。所述发酵的时间可以为从接种开始至酵母生长的衰亡期出现(即发酵时间为迟滞期、对数期加上稳定期)的时间,优选发酵的时间为50-75小时,更优选60-70小时。发酵产物乙醇可以用常规的方法,根据不同工业产品的要求(比如燃料酒精要求乙醇的纯度达99%以上)分离并精制,比如蒸馏、浓缩、除水。The fermentation temperature can be any temperature suitable for yeast growth, preferably 30-36°C, more preferably 30-33°C. The pH is 4-6, preferably 4-4.5. The time of the fermentation can be the time from the beginning of inoculation to the decay phase of yeast growth (that is, the fermentation time is the lag phase, the logarithmic phase plus the stationary phase), and the preferred fermentation time is 50-75 hours, more preferably 60-75 hours. 70 hours. The fermentation product ethanol can be separated and refined according to the requirements of different industrial products (for example, fuel alcohol requires the purity of ethanol to be more than 99%) by conventional methods, such as distillation, concentration, and water removal.
根据本发明,所述含水量小于60重量%的固体产物可以通过各种方式得到,例如可以通过对所述废液进行过滤和压榨得到的。According to the present invention, the solid product with a water content of less than 60% by weight can be obtained in various ways, for example, it can be obtained by filtering and pressing the waste liquid.
本发明的发明人对现有的从薯类原料发酵制备乙醇的废液中回收固体残渣的方法进行了细致的研究,发现现有技术中通常使用普通的压滤机对薯类原料发酵制备乙醇的废液进行过滤,在过滤时废液进入压滤机的普通滤板之间,固体颗粒被滤板的过滤介质截留在滤板之间的空间内,液体则通过过滤介质,由出孔排出压滤机外,随着过滤过程的延续,固体产物的厚度逐渐增加,脱水的阻力随之成倍增大,从而导致处理量的急剧下降,并且由于普通滤板本身性质的限制,过滤压力无法进一步的提高(一般在1MPa以下),从而无法进一步降低得到固体产物的含水量。The inventors of the present invention have carried out careful research on the existing methods of recovering solid residues from the waste liquid produced by fermenting potato raw materials to produce ethanol, and found that in the prior art, ordinary filter presses are usually used to ferment potato raw materials to produce ethanol When filtering, the waste liquid enters between the ordinary filter plates of the filter press, the solid particles are trapped in the space between the filter plates by the filter medium of the filter plate, and the liquid passes through the filter medium and is discharged from the outlet hole. Outside the filter press, with the continuation of the filtration process, the thickness of the solid product gradually increases, and the dehydration resistance increases exponentially, resulting in a sharp drop in processing capacity, and due to the limitation of the nature of the ordinary filter plate itself, the filtration pressure cannot be further increased. (generally below 1MPa), so that the water content of the solid product cannot be further reduced.
根据本发明,可以使用各种设备对所述废液进行过滤和压榨,优选情况下,可以使用隔膜压滤机来实现,隔膜压滤机具有与普通隔膜压滤机相同的过滤功能,还具有对固体产物进行压榨而使其再次脱水的功能,在隔膜压滤机中,普通滤板与隔膜滤板间隔排列,所述隔膜滤板的中间芯板与两侧隔膜压紧形成两个密封夹层,所述隔膜滤板的过滤功能与普通滤板相同,但增加了压榨功能,即,在过滤结束后将挤压介质从中间芯板入孔注入到密封层中,由于隔膜的弹性作用,能够对过滤后的固体产物进行鼓涨压榨,使固体产物再次脱水。According to the present invention, various equipment can be used to filter and squeeze the waste liquid, preferably, a diaphragm filter press can be used to achieve, the diaphragm filter press has the same filtering function as a common diaphragm filter press, and also has The function of pressing the solid product to dehydrate it again. In the diaphragm filter press, the ordinary filter plate and the diaphragm filter plate are arranged at intervals, and the middle core plate of the diaphragm filter plate is pressed with the diaphragms on both sides to form two sealed interlayers. , the filtration function of the diaphragm filter plate is the same as that of the ordinary filter plate, but the squeeze function is added, that is, after the filtration is completed, the squeeze medium is injected into the sealing layer from the inlet hole of the middle core plate, due to the elasticity of the diaphragm, it can The filtered solid product is subjected to bulge pressing to dehydrate the solid product again.
根据本发明,水溶性海藻酸酯和/或水溶性海藻酸盐的用量可以在很大范围内改变,只要能够缩短了固液分离的时间即可,优选情况下,相对于1000重量份的废液,水溶性海藻酸酯和/或水溶性海藻酸盐的用量为0.05-1重量份;进一步优选为,相对于1000重量份的废液,水溶性海藻酸酯和/或水溶性海藻酸盐的用量为0.1-0.5重量份。According to the present invention, the amount of water-soluble alginate and/or water-soluble alginate can be changed in a wide range, as long as the time of solid-liquid separation can be shortened, preferably, relative to 1000 parts by weight of waste Liquid, the consumption of water-soluble alginate and/or water-soluble alginate is 0.05-1 weight part; The consumption is 0.1-0.5 weight part.
所述水溶性海藻酸盐的种类可以在很大范围内改变,只要能够使废液中分子间的碰撞加剧,使不易沉淀的小分子结合成为大分子形成较大的絮凝物即可,优选情况下,所述水溶性海藻酸盐的相对分子量为30000-200000,相对分子量为物质的分子或特定单元的平均质量与核素12C原子质量的1/12之比。例如,所述水溶性海藻酸盐可以选自海藻酸钠、海藻酸钾和海藻酸铵中的一种或几种。符合上述要求的水溶性海藻酸盐可以通过商购得到,例如,青岛南洋海藻工业有限公司生产的海藻酸钠、青岛明月海藻集团有限公司生产的海藻酸钾以及邯郸市海洋药用海藻制品有限公司生产的海藻酸铵。The type of water-soluble alginate can be changed in a wide range, as long as the collision between molecules in the waste liquid can be intensified, and the small molecules that are not easy to precipitate can be combined into macromolecules to form larger flocs. Here, the relative molecular weight of the water-soluble alginate is 30,000-200,000, and the relative molecular weight is the ratio of the average mass of a molecule or a specific unit of a substance to 1/12 of the atomic mass of nuclide 12 C. For example, the water-soluble alginate may be selected from one or more of sodium alginate, potassium alginate and ammonium alginate. Water-soluble alginates that meet the above requirements can be obtained commercially, for example, sodium alginate produced by Qingdao Nanyang Seaweed Industry Co., Ltd., potassium alginate produced by Qingdao Mingyue Seaweed Group Co., Ltd., and Handan Ocean Medicinal Seaweed Products Co., Ltd. Production of ammonium alginate.
所述水溶性海藻酸酯的种类可以在很大范围内改变,只要能够使废液中分子间的碰撞加剧,使不易沉淀的小分子结合成为大分子形成较大的絮凝物即可,优选情况下,所述水溶性海藻酸酯的相对分子量为30000-200000,相对分子量为物质的分子或特定单元的平均质量与核素12C原子质量的1/12之比。例如,所述水溶性海藻酸酯可以选自海藻酸丙二醇酯、海藻酸乙二醇酯和海藻酸丁二醇酯中的一种或几种,优选为海藻酸丙二醇酯。符合上述要求的水溶性海藻酸酯可以通过本领域技术人员公知的方法合成得到,也可以通过商购得到,例如,青岛明月海藻集团有限公司生产的海藻酸丙二醇酯。The type of water-soluble alginate can be changed in a wide range, as long as the collision between molecules in the waste liquid can be intensified, and the small molecules that are not easy to precipitate can be combined into macromolecules to form larger flocs. Here, the relative molecular weight of the water-soluble alginate is 30,000-200,000, and the relative molecular weight is the ratio of the average mass of a molecule or a specific unit of a substance to 1/12 of the atomic mass of nuclide 12 C. For example, the water-soluble alginate may be selected from one or more of propylene glycol alginate, ethylene glycol alginate and butylene glycol alginate, preferably propylene glycol alginate. Water-soluble alginate that meets the above requirements can be synthesized by methods known to those skilled in the art, or can be obtained commercially, for example, propylene glycol alginate produced by Qingdao Mingyue Seaweed Group Co., Ltd.
优选情况下,在对废液进行固液分离之前在废液中加入水溶性海藻酸酯和水溶性海藻酸盐,在同时加入水溶性海藻酸酯和水溶性海藻酸盐时,能够进一步缩短固液分离的时间,从而进一步提高单位时间内废液的处理量。在这种情况下,水溶性海藻酸酯和水溶性海藻酸盐的用量可以在很大范围内改变,优选情况下,相对于100重量份的水溶性海藻酸酯,所述水溶性海藻酸盐的加入量为10-1000重量份。进一步优选为,相对于100重量份的水溶性海藻酸酯,所述水溶性海藻酸盐的加入量为40-300重量份。Preferably, water-soluble alginate and water-soluble alginate are added to the waste liquid before solid-liquid separation is carried out, and when adding water-soluble alginate and water-soluble alginate at the same time, the solid The time of liquid separation can further increase the treatment capacity of waste liquid per unit time. In this case, the amount of water-soluble alginate and water-soluble alginate can be changed in a wide range, preferably, with respect to 100 parts by weight of water-soluble alginate, the water-soluble alginate The addition amount of is 10-1000 parts by weight. Further preferably, relative to 100 parts by weight of the water-soluble alginate, the added amount of the water-soluble alginate is 40-300 parts by weight.
根据本发明,所述固液分离可以为常规的各种固液分离方法,如过滤,例如,可以通过压滤机来进行过滤,例如,景津压滤机集团有限公司生产的厢式压滤机。所述过滤的条件可以在很大范围内改变,优选情况下,所述过滤的条件包括过滤的压力为0.4-1MPa,过滤的时间为1-3小时。According to the present invention, the solid-liquid separation can be a variety of conventional solid-liquid separation methods, such as filtration, for example, can be filtered by a filter press, for example, the box filter press produced by Jingjin Filter Press Group Co., Ltd. machine. The filtering conditions can be changed in a wide range. Preferably, the filtering conditions include a filtering pressure of 0.4-1 MPa and a filtering time of 1-3 hours.
但是,本发明的发明人发现,使用普通的厢式压滤机对木薯发酵制备乙醇的废液进行过滤时,废液进入压滤机的厢式滤板之间,固体颗粒被滤板的过滤介质截留在滤板之间的空间内,液体则通过过滤介质,由出孔排出压滤机外,随着过滤过程的延续,固体产物的厚度逐渐增加,脱水的阻力随之成倍增大,从而导致处理量的急剧下降,并且由于厢式滤板本身性质的限制,过滤压力无法进一步的提高(一般在1MPa以下),从而无法进一步降低固体产物的含水量,后续烘干固体产物所需的能耗较高。However, the inventors of the present invention have found that when using a common box-type filter press to filter the waste liquid produced by cassava fermentation to produce ethanol, the waste liquid enters between the box-type filter plates of the filter press, and the solid particles are filtered by the filter plates. The medium is trapped in the space between the filter plates, and the liquid passes through the filter medium and is discharged out of the filter press through the outlet hole. With the continuation of the filtration process, the thickness of the solid product gradually increases, and the dehydration resistance increases exponentially. It leads to a sharp drop in processing capacity, and due to the limitation of the nature of the box filter plate itself, the filtration pressure cannot be further increased (generally below 1MPa), so that the water content of the solid product cannot be further reduced, and the energy required for subsequent drying of the solid product higher consumption.
因此,优选情况下,所述固液分离是通过对所述废液进行过滤和压榨实现的。Therefore, preferably, the solid-liquid separation is achieved by filtering and squeezing the waste liquid.
根据本发明,可以使用各种设备对所述废液进行过滤和压榨,优选情况下,可以使用隔膜压滤机来进行过滤和压榨。According to the present invention, various devices can be used to filter and squeeze the waste liquid, preferably, a membrane filter press can be used to filter and squeeze the waste liquid.
所述隔膜压滤机即具有与普通的厢式压滤机相同的过滤功能,又具有对固体产物进行压榨而使其再次脱水的功能,在隔膜压滤机中,普通的厢式滤板与隔膜滤板间隔排列,所述隔膜滤板的中间芯板与两侧隔膜压紧形成两个密封夹层,所述隔膜滤板的过滤功能与普通的厢式滤板相同,但增加了压榨功能,即,在过滤结束后将挤压介质从中间芯板入孔注入到密封层中,由于隔膜的弹性作用,能够对过滤后的固体产物进行鼓涨压榨,使固体产物再次脱水。The membrane filter press not only has the same filtering function as the ordinary box filter press, but also has the function of pressing the solid product to dehydrate it again. In the membrane filter press, the ordinary box filter plate and The diaphragm filter plates are arranged at intervals, and the middle core plate of the diaphragm filter plate is compressed with the diaphragms on both sides to form two sealed interlayers. The filtration function of the diaphragm filter plate is the same as that of the ordinary box filter plate, but the pressing function is added. That is, after the filtration is completed, the extrusion medium is injected into the sealing layer from the inlet hole of the middle core plate, and due to the elastic effect of the diaphragm, the filtered solid product can be expanded and squeezed to dehydrate the solid product again.
所述隔膜压滤机中普通的厢式滤板和隔膜滤板的数量可以根据废液的浓度进行调整,优选情况下,普通的厢式滤板的数量为50-60个,所述普通的厢式滤板可以通过商购得到,例如景津压滤机集团有限公司生产的厢式滤板;隔膜滤板的数量为50-60个,所述隔膜滤板可以通过商购得到,例如景津压滤机集团有限公司生产的1250型隔膜滤板;普通的厢式滤板与隔膜滤板间隔排列并且不同的厢式滤板的数量与隔膜滤板的数量之比为1:1;符合上述要求的隔膜压滤机可以通过商购得到,例如,景津压滤机集团有限公司生产的XM AZG600/1500×2000UB K型号的隔膜压滤机。The number of common chamber filter plates and diaphragm filter plates in the membrane filter press can be adjusted according to the concentration of waste liquid. Preferably, the number of common chamber filter plates is 50-60, and the common The box-type filter plate can be commercially obtained, such as the box-type filter plate produced by Jingjin Filter Press Group Co., Ltd.; the number of diaphragm filter plates is 50-60, and the diaphragm filter plate can be obtained commercially, such as Jingjin The 1250-type diaphragm filter plate produced by Jin Filter Press Group Co., Ltd.; ordinary box filter plates and diaphragm filter plates are arranged at intervals and the ratio of the number of different box filter plates to the number of diaphragm filter plates is 1:1; The membrane filter press required above can be purchased commercially, for example, the X M A ZG600/1500×2000U B K type membrane filter press produced by Jingjin Filter Press Group Co., Ltd.
本发明人发现,使用隔膜压滤机不但能够显著的降低压榨得到的固体产物的含水量,还能够大幅度的降低压榨去除的水中杂质的含量,减少了杂质对设备的磨损,降低了维护成本;并且去除的水中COD值也较低,减轻了环境压力。The inventors found that using a diaphragm filter press can not only significantly reduce the water content of the solid product obtained by pressing, but also greatly reduce the content of impurities in the water removed by pressing, reducing the wear and tear on the equipment by impurities and reducing maintenance costs. ; And the COD value in the removed water is also low, which reduces the environmental pressure.
本发明中,所述木薯发酵制备乙醇的废液是指通过木薯发酵来制备乙醇时,蒸馏出得到的乙醇以后,残留的固液混合物。In the present invention, the waste liquid produced by cassava fermentation to produce ethanol refers to the solid-liquid mixture remaining after distilling off the obtained ethanol when producing ethanol by cassava fermentation.
本发明中,所述过滤和压榨的条件可以在很大范围内改变,所述过滤和压榨的条件使得到的固体产物的含水量小于60重量%,优选情况下,所述过滤的条件包括过滤的压力为0.4-1MPa,过滤的时间为1-2小时;所述压榨的条件包括压榨的压力为10-25MPa,压榨的时间为0.2-1小时。In the present invention, the conditions of the filtering and squeezing can be changed in a wide range, the conditions of the filtering and squeezing make the water content of the obtained solid product less than 60% by weight, preferably, the filtering conditions include filtering The pressure of the filter is 0.4-1MPa, and the time of filtering is 1-2 hours; the conditions of the squeezing include that the pressure of squeezing is 10-25MPa, and the time of squeezing is 0.2-1 hour.
本发明中,所述压榨压力可以通过在隔膜压滤机中充入挤压介质来实现,所述挤压介质可以为隔膜压滤机常用的各种挤压介质,例如,所述挤压介质可以为压缩空气和/或水。In the present invention, the squeeze pressure can be realized by filling the squeeze medium in the membrane filter press, and the squeeze medium can be various squeeze mediums commonly used in the membrane filter press, for example, the squeeze medium Can be compressed air and/or water.
根据本发明的方法还包括将固液分离后得到的固体产物进行烘干,得到固体残渣,所述烘干的设备可以为各种常规的烘干设备,例如,沈阳远大公司生产的HZG系列烘干机和北京益民工贸有限公司生产的WJI-900B沸腾干燥机与XLS-100型闪蒸干燥机组合型烘干机。本发明中,所述烘干的条件可以为常规的烘干条件,例如,所述烘干的条件包括烘干温度为100-200℃,烘干时间为0.2-2小时;进一步优选为,烘干温度为120-150℃,烘干时间为0.5-1小时。The method according to the present invention also includes drying the solid product obtained after solid-liquid separation to obtain a solid residue. The drying equipment can be various conventional drying equipment, for example, the HZG series drying equipment produced by Shenyang Yuanda Company. Dryer and WJI-900B boiling dryer and XLS-100 flash dryer combined dryer produced by Beijing Yimin Industry and Trade Co., Ltd. In the present invention, the drying conditions may be conventional drying conditions, for example, the drying conditions include a drying temperature of 100-200°C and a drying time of 0.2-2 hours; more preferably, drying The drying temperature is 120-150°C, and the drying time is 0.5-1 hour.
下面将通过实施例对本发明做进一步的具体描述。The present invention will be further specifically described below by way of examples.
实施例1Example 1
本实施例用于说明本发明的采用木薯原料制备乙醇的方法。This example is used to illustrate the method for preparing ethanol using cassava raw material of the present invention.
(1)木薯原料的粉碎(1) Crushing of cassava raw materials
将95千克鲜木薯原料(粗4-8厘米,长20-30厘米,含水量65重量%)清洗后切成1厘米左右厚的圆片,然后使用SFSP系列锤片式粉碎机对该木薯片进行粉碎,所述粉碎的方法包括先将60千克该木薯片进行一次粉碎20分钟,得到平均颗粒直径为4.5毫米(采用美国PPS公司的Accu Sizer TM780光学粒径检测仪测定)的一次粉碎产物60千克,然后将10重量%的该一次粉碎产物60千克与剩余的35千克未经过粉碎的鲜木薯原料混合再次进行一次粉碎15分钟,得到平均颗粒直径为3毫米的一次粉碎产物,并将上述全部一次粉碎产物进行二次粉碎5分钟,得到95千克粉碎产物(该粉碎产物中木薯原料的平均颗粒直径为2毫米)。95 kilograms of fresh cassava raw materials (4-8 centimeters thick, 20-30 centimeters long, water content 65% by weight) are cleaned and cut into discs about 1 centimeter thick, and then use the SFSP series hammer mill to treat the cassava chips Pulverize, the method of described pulverization comprises first this cassava chip of 60 kilograms is carried out primary pulverization 20 minutes, obtains the primary pulverization product 60 that average particle diameter is 4.5 millimeters (Accu Sizer TM780 optical particle diameter detector adopts U.S. PPS company to measure). 60 kilograms, then 60 kilograms of this primary pulverization product of 10 weight % is mixed with the remaining 35 kilograms of fresh cassava raw materials that have not been pulverized and carried out primary pulverization for 15 minutes again to obtain a primary pulverization product with an average particle diameter of 3 millimeters, and all of the above The primary crushed product was subjected to secondary crushing for 5 minutes to obtain 95 kg of a crushed product (the average particle diameter of the cassava raw material in the crushed product was 2 mm).
取10克上述粉碎产物过滤并在45℃下烘干至恒重3.4克,称量300.0毫克该干燥后的粉碎产物,放置于重80克的100毫升干燥三角烧瓶内。向所述三角烧瓶内加入3.00毫升浓度为72重量%的硫酸溶液,搅拌1分钟。然后将三角烧瓶在30℃的水浴中放置60分钟,每隔5分钟搅拌一次以确保均匀水解。水解结束后,用去离子水使硫酸的浓度稀释到4重量%,然后用布氏漏斗过滤,共得到滤液84毫升。将20毫升滤液转移至干燥的50毫升的三角瓶中。使用2.5克碳酸钙调节该滤液的pH值至5.5,静置5小时,收集上层清液。用0.2微米滤膜过滤收集的上层清液,所得滤液用Biorad AminexHPX-87P高效液相色谱(HPLC)分析。HPLC条件:进样量20微升;流动相为0.2微米滤膜过滤并且超声振荡脱气的HPLC超纯水;流速为0.6毫升/分钟;柱温80-85℃;检测器温度80-85℃;检测器为折光率检测器;运行时间为35分钟。以0.1-4.0毫克/毫升浓度范围的D-(+)葡萄糖作为标准样品。HPLC分析得到粉碎产物酸水解液中葡萄糖浓度为3.70毫克/毫升,计算可得1克所述粉碎产物酸水解能得到重量为0.311克的葡萄糖,因为浓度为72重量%的硫酸溶液可以将粉碎产物中的淀粉全部水解成葡萄糖,因此所得葡萄糖的重量是粉碎产物中的淀粉重量的1.11倍,即1克所述粉碎产物中的淀粉含量为0.280克,则95千克粉碎产物中共含淀粉26.6千克。Take 10 grams of the above pulverized product, filter and dry at 45° C. to a constant weight of 3.4 grams, weigh 300.0 mg of the dried pulverized product, and place it in a 100 ml dry Erlenmeyer flask weighing 80 grams. Add 3.00 ml of sulfuric acid solution with a concentration of 72% by weight into the Erlenmeyer flask, and stir for 1 minute. The Erlenmeyer flask was then placed in a water bath at 30 °C for 60 minutes, stirring every 5 minutes to ensure uniform hydrolysis. After the hydrolysis, the concentration of sulfuric acid was diluted to 4% by weight with deionized water, and then filtered with a Buchner funnel to obtain a total of 84 ml of filtrate. Transfer 20 mL of the filtrate to a dry 50 mL Erlenmeyer flask. The pH value of the filtrate was adjusted to 5.5 with 2.5 g of calcium carbonate, allowed to stand for 5 hours, and the supernatant was collected. The collected supernatant was filtered with a 0.2 micron membrane filter, and the resulting filtrate was analyzed by Biorad AminexHPX-87P high performance liquid chromatography (HPLC). HPLC conditions: injection volume 20 microliters; mobile phase is HPLC ultrapure water filtered by 0.2 micron filter membrane and degassed by ultrasonic vibration; flow rate is 0.6 ml/min; column temperature 80-85°C; detector temperature 80-85°C ; The detector is a refractive index detector; the running time is 35 minutes. D-(+) glucose in the concentration range of 0.1-4.0 mg/ml is used as a standard sample. HPLC analysis obtains that the glucose concentration in the acid hydrolyzate of the pulverized product is 3.70 mg/ml, and the acid hydrolysis of 1 gram of the pulverized product can be calculated to obtain glucose with a weight of 0.311 grams, because the sulfuric acid solution with a concentration of 72% by weight can dilute the pulverized product The starch in the product is all hydrolyzed into glucose, so the weight of the glucose obtained is 1.11 times of the starch weight in the crushed product, that is, the starch content in 1 gram of the crushed product is 0.280 grams, and then 95 kg of the crushed product contains 26.6 kg of starch.
(2)酶解(2) Enzymolysis
将步骤(1)取样测试后剩余的粉碎产物与21千克水混合,调节pH值至5,加热至70℃后,以每克粉碎产物的干重计,加入20酶活力单位的α-淀粉酶(诺维信公司购得),并在70℃下保温酶解60分钟后得到酶解产物。Mix the pulverized product remaining after the sampling test in step (1) with 21 kg of water, adjust the pH value to 5, heat to 70°C, and add 20 enzyme activity units of α-amylase based on the dry weight of the pulverized product per gram (purchased by Novozymes), and the enzymolysis product was obtained after incubation at 70° C. for 60 minutes.
(3)发酵(3) fermentation
使酶解产物的温度降至33℃,以每克酶解产物的重量计,接种105菌落形成单位的酒精酵母(安琪超级酿酒高活性干酵母,湖北安琪酵母股份公司),所得混合物在33℃下于发酵罐中搅拌培养65小时,在100℃蒸馏所得发酵产物,所得蒸馏馏分在78.3℃下二次蒸馏可得乙醇13.73千克。按照下式计算乙醇产率,计算结果见表1。The temperature of the enzymatic hydrolyzate was lowered to 33°C, and inoculated with 105 colony-forming units of alcoholic yeast (Anqi Super Saccharomyces cerevisiae high-activity dry yeast, Hubei Angel Yeast Co., Ltd. Stir and cultivate in a fermenter at 33°C for 65 hours, distill the resulting fermentation product at 100°C, and distill the distilled fraction at 78.3°C to obtain 13.73 kg of ethanol. The ethanol yield was calculated according to the following formula, and the calculation results are shown in Table 1.
乙醇产率=100%×乙醇重量/木薯原料中所含淀粉的重量Ethanol yield=100%×ethanol weight/weight of starch contained in cassava raw material
取100克蒸馏乙醇后的发酵醪用布氏漏斗过滤,将20毫升滤液转移至干燥50毫升的三角瓶中,静置5小时,收集上层清液。0.2微米滤膜过滤收集的上层清液,按照上述步骤(1)所述高效液相条件,测定并计算出发酵醪中的葡萄糖共372克。并按照下式计算残糖率,计算结果见表1。Take 100 grams of fermented mash after distilling ethanol and filter it with a Buchner funnel, transfer 20 milliliters of the filtrate to a dry 50 milliliter Erlenmeyer flask, let it stand for 5 hours, and collect the supernatant. The supernatant collected by 0.2 micron filter membrane filtration, according to the high-efficiency liquid phase conditions described in the above-mentioned steps (1), measure and calculate the total 372 grams of glucose in the fermented mash. And calculate the residual sugar rate according to the following formula, and the calculation results are shown in Table 1.
残糖率=100%×发酵醪中残糖量/木薯原料中所含淀粉的重量Residual sugar rate = 100% × amount of residual sugar in fermented mash / weight of starch contained in cassava raw materials
(4)废液处理(4) Waste liquid treatment
将发酵罐中的薯类原料发酵制备乙醇的废液从发酵罐中取出,用水冲洗发酵罐,将取出的废液和冲洗后的水混合。The waste liquid produced by fermenting the potato material in the fermenter to produce ethanol is taken out from the fermenter, the fermenter is washed with water, and the taken out waste liquid is mixed with the washed water.
将15批次上述发酵的废液混合,通过水份测定仪(上海精密科学仪器有限公司,SH-10A)检测该混合废液中的含水量为95重量%。在100吨上述混合废液中加入10千克的海藻酸丙二醇酯(青岛明月海藻集团有限公司,相对分子量为40000),之后将废液加入到厢式压滤机(景津压滤机集团有限公司)中,压滤机被充满之后进行过滤,所述厢式压滤机中,普通的厢式滤板(景津压滤机集团有限公司,厢式滤板)的数量为100个,所述过滤的条件包括过滤的压力为0.8MPa,过滤的时间为2小时,得到含水量为75重量%的固体产物A1,固液分离所需的时间以及单位时间内的废液处理量(单台)如表2所示。15 batches of the above-mentioned fermented waste liquids were mixed, and the water content in the mixed waste liquids was detected to be 95% by weight by a moisture analyzer (Shanghai Precision Scientific Instrument Co., Ltd., SH-10A). Add 10 kilograms of propylene glycol alginate (Qingdao Mingyue Seaweed Group Co., Ltd., relative molecular weight is 40000) to 100 tons of the above mixed waste liquid, and then add the waste liquid to the chamber filter press (Jingjin Filter Press Group Co., Ltd. ), the filter press is filled and filtered. In the box filter press, the number of common box filter plates (Jingjin Filter Press Group Co., Ltd., box filter plates) is 100, and the The conditions of filtration include that the pressure of filtration is 0.8MPa, and the time of filtration is 2 hours to obtain a solid product A1 with a water content of 75% by weight, the time required for solid-liquid separation and the waste liquid treatment capacity per unit time (single unit) As shown in table 2.
对比例1Comparative example 1
本对比例说明采用木薯制备乙醇的参比方法。This comparative example illustrates a reference process for the production of ethanol from cassava.
按照实施例1的方法制备乙醇,不同的是,将95千克鲜木薯原料与95千克水混合(木薯原料鲜重与水的重量比为1:1)后进行一次粉碎35分钟,然后将一次粉碎产物直接进行二次粉碎5分钟,共得到190千克粉碎产物(该粉碎产物中木薯原料的平均颗粒直径为5毫米)。按照实施例1步骤(1)所述高效液相条件,测定并计算出该190千克粉碎产物中共含淀粉26.5千克。Prepare ethanol according to the method of Example 1, the difference is that 95 kilograms of fresh cassava raw materials are mixed with 95 kilograms of water (the weight ratio of cassava raw material fresh weight and water is 1:1) and then pulverized once for 35 minutes, then pulverized once The product was directly subjected to secondary crushing for 5 minutes to obtain a total of 190 kg of crushed product (the average particle diameter of the cassava raw material in the crushed product was 5 mm). According to the high-efficiency liquid phase conditions described in step (1) of Example 1, it was measured and calculated that the 190 kg pulverized product contained 26.5 kg of starch.
采用与实施例1相同的条件对取样测试后剩余的粉碎产物进行酶解,对酶解产物进行发酵,得到乙醇13.38千克。Using the same conditions as in Example 1, the remaining pulverized product after the sampling test was enzymatically hydrolyzed, and the enzymolyzed product was fermented to obtain 13.38 kg of ethanol.
取100克蒸馏乙醇后剩余的发酵醪用布氏漏斗过滤,将20毫升滤液转移至干燥50毫升的三角瓶中,静置5小时,收集上层清液。0.2微米滤膜过滤收集的上层清液,按照上述步骤(1)所述高效液相条件,测定并计算出发酵醪中的葡萄糖共583克。并按照实施例1的公式计算乙醇产率和残糖率,计算结果见表1。Take 100 grams of distilled ethanol and filter the remaining fermented mash with a Buchner funnel, transfer 20 milliliters of the filtrate to a dry 50 milliliter Erlenmeyer flask, let it stand for 5 hours, and collect the supernatant. The supernatant collected by 0.2 micron filter membrane filtration, according to the high-efficiency liquid phase conditions described in the above-mentioned steps (1), measure and calculate the total 583 grams of glucose in the fermented mash. And calculate ethanol production rate and residual sugar rate according to the formula of embodiment 1, calculation result is shown in table 1.
此外,根据与实施例1相同的方法对木薯发酵制备乙醇的废液进行过滤,不同的是没有加入海藻酸丙二醇酯,得到含水量为75重量%的参比固体产物CA1,固液分离所需的时间以及单位时间内的废液处理量(单台)如表2所示。In addition, according to the same method as in Example 1, the waste liquid produced by cassava fermentation to ethanol was filtered, except that propylene glycol alginate was not added to obtain a reference solid product CA1 with a water content of 75% by weight, which was required for solid-liquid separation. The time and the waste liquid treatment capacity per unit time (single unit) are shown in Table 2.
实施例2Example 2
本实施例用于说明本发明的采用木薯原料制备乙醇的方法。This example is used to illustrate the method for preparing ethanol using cassava raw material of the present invention.
按照实施例1的方法制备乙醇,不同的是,所述粉碎的方法包括使用SFSP系列锤片式粉碎机先将30千克鲜木薯原料进行一次粉碎12分钟,得到平均颗粒直径为5毫米的一次粉碎产物30千克,然后将5重量%的该一次粉碎产物1.5千克与剩余的25千克未经过粉碎的鲜木薯原料混合并再次进行一次粉碎10分钟,得到平均颗粒直径为4毫米的一次粉碎产物55千克,将5重量%的该一次粉碎产物2.75千克再与剩余的40千克未经过粉碎的木薯进行一次粉碎15分钟,共得到一次粉碎产物95千克,并将上述一次粉碎产物进行二次粉碎3分钟,得到95千克粉碎产物(该粉碎产物中木薯原料的平均颗粒直径为2毫米)。按照实施例1步骤(1)所述高效液相条件,测定并计算出该95千克木薯浆液中共含淀粉26.8千克。Prepare ethanol according to the method of Example 1, the difference is that the pulverizing method includes using the SFSP series hammer mill to first pulverize 30 kilograms of fresh cassava raw materials for 12 minutes to obtain a primary pulverization with an average particle diameter of 5 mm. 30 kilograms of product, then 1.5 kilograms of this primary crushing product of 5% by weight is mixed with the remaining 25 kilograms of fresh cassava raw materials that have not been crushed and once again crushed for 10 minutes to obtain 55 kilograms of primary crushing products with an average particle diameter of 4 mm 2.75 kg of the primary crushed product of 5% by weight and the remaining 40 kg of cassava that have not been crushed were crushed once for 15 minutes to obtain 95 kg of the primary crushed product, and the above-mentioned primary crushed product was subjected to secondary crushing for 3 minutes. 95 kg of a pulverized product (the average particle diameter of the cassava raw material in the pulverized product was 2 mm) was obtained. According to the high-efficiency liquid phase condition described in embodiment 1 step (1), measure and calculate that this 95 kilograms of cassava slurry contains 26.8 kilograms of starch altogether.
采用与实施例1相同的条件对取样测试后剩余的粉碎产物进行酶解,对酶解产物进行发酵,得到乙醇14.07千克。Using the same conditions as in Example 1, the remaining pulverized product after the sampling test was enzymatically hydrolyzed, and the enzymolyzed product was fermented to obtain 14.07 kg of ethanol.
取100克蒸馏乙醇后剩余的发酵醪用布氏漏斗过滤,将20毫升滤液转移至干燥50毫升的三角瓶中,静置5小时,收集上层清液。0.2微米滤膜过滤收集的上层清液,按照上述步骤(1)所述高效液相条件,测定并计算出发酵醪中的葡萄糖共348克。并按照实施例1的公式计算乙醇产率和残糖率,计算结果见表1。Take 100 grams of distilled ethanol and filter the remaining fermented mash with a Buchner funnel, transfer 20 milliliters of the filtrate to a dry 50 milliliter Erlenmeyer flask, let it stand for 5 hours, and collect the supernatant. The supernatant collected by 0.2 micron filter membrane filtration, according to the high-efficiency liquid phase conditions described in the above-mentioned steps (1), measure and calculate the total 348 grams of glucose in the fermented mash. And calculate ethanol production rate and residual sugar rate according to the formula of embodiment 1, calculation result is shown in table 1.
废液处理Waste liquid treatment
在步骤(4)中:将发酵罐中的薯类原料发酵制备乙醇的废液从发酵罐中取出,用水冲洗发酵罐,将取出的废液和冲洗后的水混合。In step (4): the waste liquid produced by fermenting the tuber material in the fermenter to prepare ethanol is taken out from the fermenter, the fermenter is rinsed with water, and the waste liquid taken out is mixed with the washed water.
将15批次上述发酵的废液混合,通过水份测定仪(上海精密科学仪器有限公司,SH-10A)检测该混合废液中的含水量为95重量%。在100吨上述混合废液中加入20千克的海藻酸钠(青岛南洋海藻工业有限公司,相对分子量为80000),之后将废液加入到厢式压滤机(景津压滤机集团有限公司)中,压滤机被充满之后进行过滤,所述厢式压滤机中,普通的厢式滤板(景津压滤机集团有限公司,厢式滤板)的数量为100个,所述过滤的条件包括过滤的压力为0.8MPa,过滤的时间为1.8小时,得到含水量为75重量%的固体产物A2,固液分离所需的时间以及单位时间内的废液处理量(单台)如表1所示。15 batches of the above-mentioned fermented waste liquids were mixed, and the water content in the mixed waste liquids was detected to be 95% by weight by a moisture analyzer (Shanghai Precision Scientific Instrument Co., Ltd., SH-10A). Add 20 kilograms of sodium alginate (Qingdao Nanyang Seaweed Industry Co., Ltd., relative molecular weight: 80,000) to 100 tons of the above mixed waste liquid, and then add the waste liquid to the chamber filter press (Jingjin Filter Press Group Co., Ltd.) Among them, the filter press is filled and filtered. In the box filter press, the number of common box filter plates (Jingjin Filter Press Group Co., Ltd., box filter plates) is 100. The filter The pressure that the condition comprises filtration is 0.8MPa, and the time of filtration is 1.8 hours, obtains water content and is the solid product A2 of 75% by weight, the time required for solid-liquid separation and the waste liquid treatment capacity (single unit) in unit time such as Table 1 shows.
实施例3Example 3
本实施例用于说明本发明的采用木薯原料制备乙醇的方法。This example is used to illustrate the method for preparing ethanol using cassava raw material of the present invention.
按照实施例1的方法制备乙醇,不同的是,所述粉碎的方法包括使用SFSP系列锤片式粉碎机先将50千克鲜木薯进行一次粉碎15分钟,得到平均颗粒直径为5.5毫米的一次粉碎产物50千克,然后将8重量%的该一次粉碎产物4千克与剩余的45千克未粉碎的鲜木薯原料混合并再次进行一次粉碎15分钟,将该粉碎产物与第一次粉碎后的粉碎产物混合共得到平均颗粒直径为4毫米的一次粉碎产物95千克,并将上述一次粉碎产物进行二次粉碎3分钟,得到95千克粉碎产物木薯浆液(木薯原料平均颗粒直径为2毫米)。按照实施例1步骤(1)所述高效液相条件,测定并计算出该95千克粉碎产物中共含淀粉26.6千克。Prepare ethanol according to the method of Example 1, the difference is that the pulverizing method includes using the SFSP series hammer mill to first pulverize 50 kilograms of fresh cassava for 15 minutes to obtain a pulverized product with an average particle diameter of 5.5 mm 50 kilograms, then 4 kilograms of this primary pulverization product of 8 weight % is mixed with the remaining 45 kilograms of fresh cassava raw materials that are not pulverized and pulverized once again for 15 minutes, and the pulverized product is mixed with the pulverized product after the first pulverization Obtaining 95 kilograms of primary crushed products with an average particle diameter of 4 mm, and performing secondary crushing on the above primary crushed products for 3 minutes to obtain 95 kg of crushed product cassava slurry (cassava raw material average particle diameter is 2 mm). According to the high-efficiency liquid phase conditions described in step (1) of Example 1, it was measured and calculated that the 95 kg pulverized product contained 26.6 kg of starch.
采用与实施例1相同的条件对取样测试后剩余的粉碎产物进行酶解,对酶解产物进行发酵,得到乙醇13.81千克。Using the same conditions as in Example 1, the remaining pulverized product after the sampling test was enzymatically hydrolyzed, and the enzymolyzed product was fermented to obtain 13.81 kg of ethanol.
取100克蒸馏乙醇后剩余的发酵醪用布氏漏斗过滤,将20毫升滤液转移至干燥50毫升的三角瓶中,静置5小时,收集上层清液。0.2微米滤膜过滤收集的上层清液,按照上述步骤(1)所述高效液相条件,测定并计算出发酵醪中的葡萄糖共372克。并按照实施例1的公式计算乙醇产率和残糖率,计算结果见表1。Take 100 grams of distilled ethanol and filter the remaining fermented mash with a Buchner funnel, transfer 20 milliliters of the filtrate to a dry 50 milliliter Erlenmeyer flask, let it stand for 5 hours, and collect the supernatant. The supernatant collected by 0.2 micron filter membrane filtration, according to the high-efficiency liquid phase conditions described in the above-mentioned steps (1), measure and calculate the total 372 grams of glucose in the fermented mash. And calculate ethanol production rate and residual sugar rate according to the formula of embodiment 1, calculation result is shown in table 1.
废液处理Waste liquid treatment
将发酵罐中的薯类原料发酵制备乙醇的废液从发酵罐中取出,用水冲洗发酵罐,将取出的废液和冲洗后的水混合。The waste liquid produced by fermenting the potato material in the fermenter to produce ethanol is taken out from the fermenter, the fermenter is washed with water, and the taken out waste liquid is mixed with the washed water.
将15批次上述发酵的废液混合,通过水份测定仪(上海精密科学仪器有限公司,SH-10A)检测该混合废液中的含水量为95重量%。在100吨上述混合废液中加入10千克的海藻酸铵(邯郸市海洋药用海藻制品有限公司,相对分子量为100000)和10千克的海藻酸丙二醇酯(青岛明月海藻集团有限公司,相对分子量为50000),之后将废液加入到厢式压滤机(景津压滤机集团有限公司)中,压滤机被充满之后进行过滤,所述厢式压滤机中,普通的厢式滤板(景津压滤机集团有限公司,厢式滤板)的数量为100个,所述过滤的条件包括过滤的压力为0.8MPa,过滤的时间为1.8小时,得到固体产物A3。15 batches of the above-mentioned fermented waste liquids were mixed, and the water content in the mixed waste liquids was detected to be 95% by weight by a moisture analyzer (Shanghai Precision Scientific Instrument Co., Ltd., SH-10A). Add 10 kilograms of ammonium alginate (Handan Ocean Medicinal Seaweed Products Co., Ltd., relative molecular weight is 100000) and 10 kilograms of propylene glycol alginate (Qingdao Mingyue Seaweed Group Co., Ltd., relative molecular weight: 50000), then the waste liquid is added to the box filter press (Jingjin Filter Press Group Co., Ltd.), and the filter press is filled and then filtered. In the box filter press, the common box filter plate (Jingjin Filter Press Group Co., Ltd., box-type filter plate) was 100, and the filtration conditions included that the filtration pressure was 0.8 MPa, and the filtration time was 1.8 hours to obtain solid product A3.
通过水份测定仪(上海精密科学仪器有限公司,SH-10A)检测固体产物A3的含水量,结果如表3所示。The water content of the solid product A3 was detected by a moisture analyzer (Shanghai Precision Scientific Instrument Co., Ltd., SH-10A), and the results are shown in Table 3.
将得到的固体产物A3放入到气流滚筒型烘干机中(郑州万谷机械有限公司,JB/T10279-2001)进行烘干,烘干的温度为180℃,得到固体残渣,通过水份测定仪(上海精密科学仪器有限公司,SH-10A)检测固体残渣的含水量,固体残渣的含水量和烘干的能耗如表3所示。Put the obtained solid product A3 into an air-flow drum dryer (Zhengzhou Wangu Machinery Co., Ltd., JB/T10279-2001) for drying at a temperature of 180° C. to obtain a solid residue, which is determined by moisture content An instrument (Shanghai Precision Scientific Instrument Co., Ltd., SH-10A) detects the water content of the solid residue, and the water content of the solid residue and the energy consumption of drying are shown in Table 3.
所述能耗是指烘干除去1千克的水所消耗的煤,单位为千克/千克。The energy consumption refers to the coal consumed to dry and remove 1 kg of water, and the unit is kg/kg.
实施例4Example 4
本实施例用于说明本发明的采用木薯原料制备乙醇的方法。This example is used to illustrate the method for preparing ethanol using cassava raw material of the present invention.
按照实施例1的方法制备乙醇,不同的是,将61千克鲜木薯原料切片后与40千克干木薯片(含水量为13重量%)和65千克水混合后得到的166千克混合物进行粉碎,粉碎的方法包括使用SFSP系列锤片式粉碎机先将40千克木薯原料混合物进行一次粉碎20分钟,得到木薯平均颗粒直径为5.5毫米的一次粉碎产物40千克,然后将8重量%的该粉碎产物3.2千克与剩余的木薯原料混合物中的30千克混合并重新进行一次粉碎10分钟,得到木薯平均颗粒直径为5毫米的一次粉碎产物共70千克,将该一次粉碎产物的10重量%的该粉碎产物7千克再与剩余的木薯原料混合物中的40千克混合物进行一次粉碎10分钟,得到平均颗粒直径为4毫米的一次粉碎产物共110千克,将该一次粉碎产物的6重量%的该粉碎产物6.6千克再与剩余的木薯原料混合物中的56千克混合物进行一次粉碎10分钟,得到平均颗粒直径为2.5毫米的一次粉碎产物166千克,并将上述全部一次粉碎产物进行二次粉碎5分钟,得到166千克粉碎产物(该粉碎产物中木薯原料的平均颗粒直径为1.6毫米)。按照实施例1步骤(1)所述高效液相条件,测得并计算出166千克粉碎产物中共含淀粉43.65千克。Prepare ethanol according to the method for Example 1, the difference is that 166 kilograms of mixture obtained after 61 kilograms of fresh cassava slices are mixed with 40 kilograms of dry cassava chips (water content is 13% by weight) and 65 kilograms of water are pulverized, pulverized The method comprises using a SFSP series hammer mill to first crush 40 kg of the cassava raw material mixture for 20 minutes to obtain 40 kg of the primary crushed product with an average particle diameter of cassava of 5.5 mm, and then crush 3.2 kg of the crushed product with 8% by weight Mix with 30 kilograms in the remaining cassava raw material mixture and carry out primary crushing 10 minutes again, obtain cassava average particle diameter and be 70 kilograms of primary crushing products of 5 millimeters altogether, this crushing product 7 kilograms of 10 weight % of this primary crushing products Carry out primary crushing 10 minutes again with 40 kilograms of mixtures in remaining cassava raw material mixture, obtain average particle diameter and be 110 kilograms of primary crushing products of 4 millimeters altogether, this primary crushing product 6.6 kilograms of this crushing product of 6 weight % is mixed again 56 kilograms of mixtures in the remaining cassava raw material mixture were pulverized once for 10 minutes to obtain 166 kilograms of primary pulverized products with an average particle diameter of 2.5 millimeters, and all of the above-mentioned pulverized products were carried out secondary pulverized for 5 minutes to obtain 166 kilograms of pulverized products ( The average particle diameter of the cassava raw material in this pulverized product was 1.6 mm). According to the high-efficiency liquid phase conditions described in step (1) of Example 1, it was measured and calculated that 166 kg of pulverized products contained 43.65 kg of starch.
采用与实施例1相同的条件对取样测试后的粉碎产物进行酶解,不同的是,酶解时加水量为30千克,对酶解产物进行发酵,得到乙醇23.09千克。The pulverized product after sampling and testing was enzymatically hydrolyzed using the same conditions as in Example 1. The difference was that the amount of water added during enzymolysis was 30 kg, and the enzymolyzed product was fermented to obtain 23.09 kg of ethanol.
取100克蒸馏乙醇后剩余的发酵醪用布氏漏斗过滤,将20毫升滤液转移至干燥50毫升的三角瓶中,静置5小时,收集上层清液。0.2微米滤膜过滤收集的上层清液,按照上述步骤(1)所述高效液相条件,测定并计算出发酵醪中的葡萄糖共592克。并按照实施例1的公式计算乙醇产率和残糖率,计算结果见表1。Take 100 grams of distilled ethanol and filter the remaining fermented mash with a Buchner funnel, transfer 20 milliliters of the filtrate to a dry 50 milliliter Erlenmeyer flask, let it stand for 5 hours, and collect the supernatant. The supernatant collected by 0.2 micron filter membrane filtration, according to the high-efficiency liquid phase conditions described in the above-mentioned steps (1), measure and calculate the total 592 grams of glucose in the fermented mash. And calculate ethanol production rate and residual sugar rate according to the formula of embodiment 1, calculation result is shown in table 1.
废液处理Waste liquid treatment
根据与实施例3相同的方法对木薯发酵制备乙醇的废液进行过滤,不同的是将废液加入到隔膜压滤机(景津压滤机集团有限公司,XM AZG600/1500×2000UB K)中进行固液分离,所述隔膜压滤机中,用50个隔膜滤板(景津压滤机集团有限公司,1250型)替换50个普通的厢式滤板(景津压滤机集团有限公司,厢式滤板),并且普通的厢式滤板与隔膜滤板间隔排列;所述过滤的条件包括过滤的压力为0.8MPa,过滤的时间为1小时;之后在隔膜滤板中充入挤压介质空气,对过滤后的固体产物进行压榨,所述压榨的压力为10MPa,压榨的时间为0.8小时,得到固体产物A4。According to the same method as Example 3, the waste liquid prepared by cassava fermentation to ethanol is filtered, the difference is that the waste liquid is added to a membrane filter press (Jingjin Filter Press Group Co., Ltd., X M A ZG600/1500 × 2000U B Carry out solid-liquid separation in K ), in described diaphragm filter press, replace 50 common chamber filter plates (Jingjin filter press) with 50 diaphragm filter plates (Jingjin Filter Press Group Co., Ltd., 1250 type) Group Co., Ltd., box-type filter plate), and the common box-type filter plate and the diaphragm filter plate are arranged at intervals; the conditions of the filtration include that the pressure of filtration is 0.8MPa, and the time of filtration is 1 hour; after that, in the membrane filter plate Fill the squeeze medium with air, and squeeze the filtered solid product, the pressure of the squeeze is 10 MPa, and the squeeze time is 0.8 hours, to obtain the solid product A4.
通过水份测定仪(上海精密科学仪器有限公司,SH-10A)检测固体产物A4的含水量,结果如表2所示。The water content of the solid product A4 was detected by a moisture analyzer (Shanghai Precision Scientific Instrument Co., Ltd., SH-10A), and the results are shown in Table 2.
将得到的固体产物A4放入到气流滚筒型烘干机中(郑州万谷机械有限公司,JB/T10279-2001)进行烘干,烘干的温度为120℃,得到固体残渣,通过水份测定仪(上海精密科学仪器有限公司,SH-10A)检测固体残渣的含水量,固体残渣的含水量和烘干的能耗如表2所示。Put the obtained solid product A4 into an air-flow drum dryer (Zhengzhou Wangu Machinery Co., Ltd., JB/T10279-2001) for drying. The drying temperature is 120° C. to obtain a solid residue, which is determined by moisture content An instrument (Shanghai Precision Scientific Instrument Co., Ltd., SH-10A) detects the water content of the solid residue, and the water content of the solid residue and the energy consumption of drying are shown in Table 2.
所述能耗是指烘干除去1千克的水所消耗的煤,单位为千克/千克。The energy consumption refers to the coal consumed to dry and remove 1 kg of water, and the unit is kg/kg.
表1Table 1
本发明的方法不但消耗水的量少,能够在短时间内完成粉碎,消耗的能量较少,设备的利用率较高,粉碎效率较高,同时采用本发明的二次粉碎的方法能够很好的控制粉碎后得到的粉碎产物中薯类原料颗粒的粒径,使最终得到的薯类原料颗粒的粒径小且均匀。The method of the present invention not only consumes less water, but can complete the crushing in a short time, consumes less energy, has a higher utilization rate of the equipment, and has a higher crushing efficiency. Control the particle size of potato raw material particles in the pulverized product obtained after crushing, so that the particle size of the finally obtained potato raw material particles is small and uniform.
从上表1中的数据可以看出,采用本发明提供的薯类原料制备乙醇的方法得到的乙醇的淀粉乙醇的产率明显高于由参比方法的淀粉乙醇产率,且与现有技术比较,本发明的制备乙醇的方法的残糖率大大降低。As can be seen from the data in the above table 1, the starch ethanol yield of ethanol obtained by the method for preparing ethanol from potato raw materials provided by the invention is significantly higher than the starch ethanol yield of the reference method, and is different from that of the prior art In comparison, the residual sugar rate of the method for preparing ethanol of the present invention is greatly reduced.
表2Table 2
从上表2可以看出,本发明的从木薯发酵制备乙醇的废液中回收固体残渣的方法,显著地缩短了固液分离的时间,在无需增加新设备的情况下显著地提高了单位时间内废液的处理量,从而解决了导致木薯发酵制备乙醇的装置的运行负荷较低的瓶颈,提高了木薯发酵制备乙醇的装置的生产能力。As can be seen from the above table 2, the method for reclaiming solid residues from the waste liquid of ethanol produced by cassava fermentation of the present invention significantly shortens the time of solid-liquid separation, and significantly improves the unit time without adding new equipment. The processing capacity of the internal waste liquid is reduced, thereby solving the bottleneck of the lower operating load of the device for producing ethanol by cassava fermentation, and improving the production capacity of the device for producing ethanol by cassava fermentation.
表3table 3
从上表3可以看出,本发明实施例4得到的固体产物A4的含水量为55重量%,而实施例3得到的固体产物A3的含水量则高达74重量%,说明通过使用隔膜压滤机对废液进行过滤和压榨能够显著地降低得到的固体产物的含水量,并且实施例4与实施例3相比,烘干所需的能耗大幅度的减少,说明说明通过使用隔膜压滤机对废液进行过滤和压榨能够大幅度的降低回收固体残渣所需的能耗。As can be seen from the above table 3, the water content of the solid product A4 obtained in Example 4 of the present invention is 55% by weight, while the water content of the solid product A3 obtained in Example 3 is as high as 74% by weight. The machine can significantly reduce the water content of the solid product obtained by filtering and squeezing the waste liquid, and compared with Example 3, the energy consumption required for drying is greatly reduced in Example 4, which shows that by using membrane filter press Filtering and pressing the waste liquid by the machine can greatly reduce the energy consumption required to recover the solid residue.
Claims (14)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN200810222820XA CN101676394B (en) | 2008-09-19 | 2008-09-19 | Method for preparing alcohol by utilizing potato materials |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN200810222820XA CN101676394B (en) | 2008-09-19 | 2008-09-19 | Method for preparing alcohol by utilizing potato materials |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101676394A CN101676394A (en) | 2010-03-24 |
CN101676394B true CN101676394B (en) | 2012-07-04 |
Family
ID=42029102
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN200810222820XA Active CN101676394B (en) | 2008-09-19 | 2008-09-19 | Method for preparing alcohol by utilizing potato materials |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN101676394B (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09187774A (en) | 1995-12-29 | 1997-07-22 | Nousan Giken:Kk | Method for processing high concentration distillation waste liquid accompanied with producing alcohols |
CN1966695A (en) * | 2006-11-10 | 2007-05-23 | 江南大学 | Circulation production process for alcohol with potatoes as main materials |
CN101195836A (en) * | 2008-01-04 | 2008-06-11 | 广西明阳生化科技股份有限公司 | Novel technique for producing manioc waste ethanol |
-
2008
- 2008-09-19 CN CN200810222820XA patent/CN101676394B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09187774A (en) | 1995-12-29 | 1997-07-22 | Nousan Giken:Kk | Method for processing high concentration distillation waste liquid accompanied with producing alcohols |
CN1966695A (en) * | 2006-11-10 | 2007-05-23 | 江南大学 | Circulation production process for alcohol with potatoes as main materials |
CN101195836A (en) * | 2008-01-04 | 2008-06-11 | 广西明阳生化科技股份有限公司 | Novel technique for producing manioc waste ethanol |
Non-Patent Citations (1)
Title |
---|
姚文娟等.絮凝法处理酒精废液的研究.《酿酒科技》.2001,全文. * |
Also Published As
Publication number | Publication date |
---|---|
CN101676394A (en) | 2010-03-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Chang et al. | Comparison of batch and fed-batch fermentations using corncob hydrolysate for bioethanol production | |
CN101487025B (en) | Method for preparing ethanol from tuber crops raw material | |
CN101851650A (en) | A kind of saccharification method of cellulose raw material | |
CN100489108C (en) | Process for producing ethanol by using potatoes as raw material | |
CN101195836A (en) | Novel technique for producing manioc waste ethanol | |
CN101265485A (en) | A method for synchronously producing ethanol by using Jerusalem artichoke raw material saccharification and fermentation | |
CN101701225A (en) | A preparation method of bioethanol using seaweed processing waste as raw material | |
CN102031276B (en) | Method for producing hydrogen by fermenting organism and alkali mat composite pretreated straw fiber raw erial at two steps | |
CN105543289A (en) | Oak acorn tannin extraction and starch thick mash fermentation coupling method | |
CN109182418B (en) | Method for saccharifying straw through microbial enzymolysis | |
CN103421851A (en) | Method for preparing sugar and ethanol by use of sweet potato wastes | |
CN101676393B (en) | Method for preparing alcohol by utilizing potato materials | |
CN107988275B (en) | A new process for fermenting cassava raw meal to produce alcohol | |
CN101676394B (en) | Method for preparing alcohol by utilizing potato materials | |
CN101676397B (en) | Method for preparing alcohol by utilizing potato materials | |
CN101988077B (en) | Method for preparing ethanol from potato raw material | |
CN112159762B (en) | Fusarium oxysporum SWH-3 and method for producing diosgenin by fermentation of fusarium oxysporum SWH-3 | |
CN101487027B (en) | Method for preparing ethanol from tuber crops raw material | |
CN101487024B (en) | Method for preparing ethanol from tuber crops raw material | |
CN107142297A (en) | A kind of synchronous saccharification common fermentation method | |
CN101487026B (en) | Method for preparing ethanol from tuber crops raw material | |
CN102206681A (en) | Method for producing ethanol through synchronous fermentation of seaweed processing waste | |
CN101381743A (en) | Method for producing hydrogen and ethanol from straw-like biomass through solid-state enzymatic hydrolysis pretreatment | |
CN101676398B (en) | Method for preparing alcohol by utilizing potato materials | |
CN115181681B (en) | A kind of microbial bacterial agent for preparing bioethanol, preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |