CN114213378A - Environment-friendly glucolactone processing method - Google Patents
Environment-friendly glucolactone processing method Download PDFInfo
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- CN114213378A CN114213378A CN202111581379.6A CN202111581379A CN114213378A CN 114213378 A CN114213378 A CN 114213378A CN 202111581379 A CN202111581379 A CN 202111581379A CN 114213378 A CN114213378 A CN 114213378A
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- Prior art keywords
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- gluconolactone
- sodium gluconate
- wastewater
- percent
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- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 title claims abstract description 61
- 238000003672 processing method Methods 0.000 title claims abstract description 11
- 239000002351 wastewater Substances 0.000 claims abstract description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 74
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000176 sodium gluconate Substances 0.000 claims abstract description 60
- 235000012207 sodium gluconate Nutrition 0.000 claims abstract description 60
- 229940005574 sodium gluconate Drugs 0.000 claims abstract description 60
- 239000012452 mother liquor Substances 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 45
- 235000012209 glucono delta-lactone Nutrition 0.000 claims abstract description 41
- 229960003681 gluconolactone Drugs 0.000 claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 29
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims abstract description 26
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims abstract description 26
- 239000000174 gluconic acid Substances 0.000 claims abstract description 26
- 235000012208 gluconic acid Nutrition 0.000 claims abstract description 26
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 19
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract 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 claims abstract description 13
- 239000008103 glucose Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000004064 recycling Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 58
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 37
- 238000002360 preparation method Methods 0.000 claims description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 239000004567 concrete Substances 0.000 claims description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 241000209094 Oryza Species 0.000 claims description 18
- 235000007164 Oryza sativa Nutrition 0.000 claims description 18
- 235000009566 rice Nutrition 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000005119 centrifugation Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 229920005646 polycarboxylate Polymers 0.000 claims description 14
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 229920002472 Starch Polymers 0.000 claims description 9
- 238000000909 electrodialysis Methods 0.000 claims description 9
- 235000013336 milk Nutrition 0.000 claims description 9
- 239000008267 milk Substances 0.000 claims description 9
- 210000004080 milk Anatomy 0.000 claims description 9
- 230000008929 regeneration Effects 0.000 claims description 9
- 238000011069 regeneration method Methods 0.000 claims description 9
- 235000019698 starch Nutrition 0.000 claims description 9
- 239000008107 starch Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 239000008030 superplasticizer Substances 0.000 claims description 8
- 239000002518 antifoaming agent Substances 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 7
- 238000013329 compounding Methods 0.000 claims description 7
- 238000000855 fermentation Methods 0.000 claims description 7
- 230000004151 fermentation Effects 0.000 claims description 7
- 238000005342 ion exchange Methods 0.000 claims description 7
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 6
- 229930003268 Vitamin C Natural products 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 235000020195 rice milk Nutrition 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- 235000019154 vitamin C Nutrition 0.000 claims description 6
- 239000011718 vitamin C Substances 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010276 construction Methods 0.000 claims description 5
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000004382 Amylase Substances 0.000 claims description 3
- 102000013142 Amylases Human genes 0.000 claims description 3
- 108010065511 Amylases Proteins 0.000 claims description 3
- 108090000790 Enzymes Proteins 0.000 claims description 3
- 102000004190 Enzymes Human genes 0.000 claims description 3
- 239000004366 Glucose oxidase Substances 0.000 claims description 3
- 108010015776 Glucose oxidase Proteins 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 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 claims description 3
- 235000019418 amylase Nutrition 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229940088598 enzyme Drugs 0.000 claims description 3
- 229940116332 glucose oxidase Drugs 0.000 claims description 3
- 235000019420 glucose oxidase Nutrition 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 108090000623 proteins and genes Proteins 0.000 claims description 3
- 102000004169 proteins and genes Human genes 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 230000001932 seasonal effect Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 abstract description 5
- 239000010865 sewage Substances 0.000 abstract description 4
- 230000001172 regenerating effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 50
- 238000004364 calculation method Methods 0.000 description 9
- 239000004568 cement Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229930003231 vitamin Natural products 0.000 description 4
- 239000011782 vitamin Substances 0.000 description 4
- 235000013343 vitamin Nutrition 0.000 description 4
- 229940088594 vitamin Drugs 0.000 description 4
- 150000003722 vitamin derivatives Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- -1 hydrogen ions Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HOOWDPSAHIOHCC-UHFFFAOYSA-N dialuminum tricalcium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[Al+3].[Al+3].[Ca++].[Ca++].[Ca++] HOOWDPSAHIOHCC-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000000182 glucono-delta-lactone Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011513 prestressed concrete Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/30—Oxygen atoms, e.g. delta-lactones
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- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/166—Macromolecular compounds comprising sulfonate or sulfate groups obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
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- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/02—Monosaccharides
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- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
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- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/20—Preparation of compounds containing saccharide radicals produced by the action of an exo-1,4 alpha-glucosidase, e.g. dextrose
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- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
- C12P7/58—Aldonic, ketoaldonic or saccharic acids
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
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Abstract
The processing method of the environment-friendly glucolactone comprises the following steps: step S1: preparing a glucose solution; step S2: preparing a sodium gluconate solution; step S3: purifying the sodium gluconate solution; step S4: preparing a gluconic acid solution; step S5: preparing a glucolactone wet product; step S6: preparing a finished product of glucolactone; step S7: and (5) recycling the wastewater. According to the invention, the wastewater generated by centrifuging the sodium gluconate, the sodium sulfate wastewater generated after regenerating the resin and the wastewater generated by centrifuging the gluconolactone are used as water for producing the aliphatic water reducer mother liquor and the polycarboxylic acid water reducer mother liquor, and can replace part of raw and auxiliary materials of the water reducer, so that zero discharge of the wastewater generated in the process of producing the gluconolactone by adopting a sodium salt method is realized, the comprehensive treatment cost of the sewage of enterprises is greatly reduced, and zero pollution to the environment is realized.
Description
Technical Field
The invention belongs to the technical field of glucolactone processing, and particularly relates to an environment-friendly glucolactone processing method.
Background
The Glucono-delta-lactone is called gluconic acid-delta-lactone for short, is white crystal or crystalline powder in appearance, is slightly soluble in ethanol, is very easy to dissolve in water, is slowly hydrolyzed at room temperature or lower temperature, and is accelerated along with the rise of the temperature. Gluconolactone is currently an internationally recognized non-toxic food additive that is widely used in the food industry.
In the prior art, a sodium salt method is generally adopted to produce gluconolactone, and the method comprises the steps of firstly converting gluconic acid generated by fermentation into sodium gluconate, then generating gluconic acid through ion exchange, and finally concentrating and crystallizing to obtain the gluconolactone. However, the method can generate more industrial wastewater in the production process, and the wastewater not only causes the cost of the comprehensive treatment of the sewage of enterprises to be greatly increased, but also causes certain pollution to the environment.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an environment-friendly glucolactone processing method, which comprises the following specific technical scheme:
the processing method of the environment-friendly glucolactone comprises the following steps:
step S1: preparation of glucose solution
Firstly, introducing running water into starch to generate starch milk or introducing running water into rice to grind the rice into rice milk, secondly, adding amylase into the starch milk or the rice milk to adjust the milk and liquefy and preserve heat, then, carrying out rice residue removal treatment through solid-liquid separation, and adding saccharifying enzyme into the liquid after removing the residues to saccharify the liquid to generate glucose solution;
step S2: preparation of sodium gluconate solution
Adding glucose oxidase into the glucose solution prepared in the step S1, introducing oxygen into the glucose solution for fermentation treatment, and adding sodium hydroxide after fermentation to react to generate a sodium gluconate solution;
step S3: purification of sodium gluconate solution
Firstly, sequentially filtering, concentrating, crystallizing and centrifuging the sodium gluconate solution prepared in the step S2, and storing the waste water containing part of sodium gluconate generated after centrifugation for later use; then, sequentially dissolving, decoloring, filtering and ultrafiltering the sodium gluconate generated after centrifugation to obtain a purified sodium gluconate solution;
step S4: preparation of gluconic acid solution
Introducing the sodium gluconate solution purified in the step S3 into a continuous ion exchange system filled with strong acid cation resin to convert the sodium gluconate solution into a gluconic acid solution, and simultaneously storing sodium sulfate wastewater generated after the exchange of the strong acid cation resin is subjected to sulfuric acid regeneration treatment for later use;
step S5: preparation of gluconolactone wet product
Concentrating and crystallizing the gluconic acid solution prepared in the step S4 to obtain a glucolactone wet product;
step S6: preparation of finished product of gluconolactone
Firstly, centrifuging the gluconolactone wet product prepared in the step S5, and storing the waste water containing part of the gluconolactone generated after centrifugation for later use; then, carrying out vacuum drying and sieving treatment on the gluconolactone generated after centrifugation, and adding an anticaking agent to obtain a finished product of the gluconolactone;
step S7: waste water recovery and utilization
And (3) recycling the wastewater containing part of the sodium gluconate generated in the step S3, the sodium sulfate wastewater generated in the step S4 and the wastewater containing part of the gluconolactone generated in the step S6 in a centralized manner, and mixing the three types of wastewater to prepare the aliphatic water reducer mother liquor and the polycarboxylic acid water reducer mother liquor by replacing a common water source.
Further, the preparation method of the aliphatic water reducer mother liquor comprises the following steps:
firstly, respectively putting 45-50% of the wastewater and 14-16.5% of sodium sulfite solid in the step S7 into a reaction kettle according to the mass percentage for stirring and dissolving treatment;
secondly, according to the mass percentage, 26-28.5 percent of formaldehyde and 10-11.5 percent of acetone are respectively put into a reaction kettle to be stirred and reacted to prepare mother liquor of the aliphatic water reducing agent;
wherein, the acetone which is partially volatilized during stirring is condensed and recycled to the reaction kettle for reuse.
Further, the preparation method of the polycarboxylate superplasticizer mother liquor comprises the following steps:
firstly, according to the mass percentage, 20 to 22 percent of the waste water, 0.15 to 0.18 percent of mercaptopropionic acid and 0.07 to 0.12 percent of food-grade vitamin C in the step S7 are respectively put into a first reaction kettle, and stirred and mixed to form material A, or 20 to 22 percent of the waste water, 0.18 to 0.25 percent of mercaptoethanol and 0.07 to 0.12 percent of food-grade vitamin C;
secondly, according to the mass percentage, 15 to 18 percent of the waste water, 3.8 to 4.5 percent of the acrylic acid, or 15 to 18 percent of the waste water, 1 to 1.5 percent of the acrylic acid and 3.5 to 4.5 percent of the hydroxyethyl acrylate in the step S7 are respectively put into a second reaction kettle to be stirred and mixed to form a material B;
and thirdly, respectively putting 15-20% of the wastewater and 33-36% of unsaturated monomers in the step S7 into a third reaction kettle according to the mass percentage, stirring and dissolving, adding 0.5-0.8% of hydrogen peroxide for catalytic reaction, and then respectively adding the material A and the material B into the third reaction kettle in a dropwise manner for stirring reaction to prepare the polycarboxylic acid water reducer mother liquor.
Further, the unsaturated monomer is any one of methyl allyl polyoxyethylene ether or isoamylol polyoxyethylene ether.
Further, the aliphatic water reducer mother liquor and the polycarboxylate water reducer mother liquor are compounded to form an aliphatic water reducer finished product and a polycarboxylate water reducer finished product according to concrete strength and seasonal construction requirements by adding white sugar, an air entraining agent, a defoaming agent, sodium gluconate mother liquor and the wastewater in the step S7.
Further, the rice residue generated in the step S1 is cleaned and dried to prepare rice protein powder, and the rice residue wastewater generated during cleaning replaces part of the defoaming agent to be put into the compounding of the finished water reducing agent.
Further, the anticaking agent in the step S6 is silica powder having a particle size of 1500 mesh or more.
Further, the preparation of the gluconic acid solution in the step S4 may be performed by introducing the gluconic acid solution into a membrane treatment system, and directly converting the sodium gluconate solution after the volume purification in the step S3 into the gluconic acid solution and a sodium hydroxide solution by using a bipolar membrane electrodialysis method; and concentrating and crystallizing the gluconic acid solution to obtain a finished product of glucolactone, concentrating the sodium hydroxide solution, and putting the concentrated sodium hydroxide solution into the step S2 to react to generate the sodium gluconate solution.
The invention has the beneficial effects that:
according to the invention, the wastewater generated by centrifuging the sodium gluconate, the sodium sulfate wastewater generated after regenerating the resin and the wastewater generated by centrifuging the gluconolactone are used as water for producing the aliphatic water reducer mother liquor and the polycarboxylic acid water reducer mother liquor, and can replace part of raw and auxiliary materials of the water reducer, so that zero discharge of the wastewater generated in the process of producing the gluconolactone by adopting a sodium salt method is realized, the comprehensive treatment cost of the sewage of enterprises is greatly reduced, and zero pollution to the environment is realized.
Drawings
FIG. 1 shows a flow chart of the process for preparing gluconolactone according to the invention;
FIG. 2 shows a flow chart of a production process of the aliphatic water-reducing agent in the invention;
FIG. 3 shows a flow chart of a production process of the polycarboxylic acid water-reducing agent of the present invention;
FIG. 4 is a schematic diagram showing the operation of the bipolar membrane electrodialysis method for producing gluconic acid in the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in figure 1, the processing method of the environment-friendly glucolactone comprises the following steps:
step S1: preparation of glucose solution
Firstly, introducing running water into starch to generate starch milk or introducing running water into rice to grind the rice into rice milk, secondly, adding amylase into the starch milk or the rice milk to adjust the milk and liquefy and preserve heat, then, carrying out rice residue removal treatment through solid-liquid separation, and adding saccharifying enzyme into the liquid after removing the residues to saccharify the liquid to generate glucose solution;
step S2: preparation of sodium gluconate solution
Adding glucose oxidase into the glucose solution prepared in the step S1, introducing oxygen into the glucose solution for fermentation treatment, and adding sodium hydroxide after fermentation to react to generate a sodium gluconate solution;
step S3: purification of sodium gluconate solution
Firstly, sequentially filtering, concentrating, crystallizing and centrifuging the sodium gluconate solution prepared in the step S2, and storing the waste water containing part of sodium gluconate generated after centrifugation for later use; then, sequentially dissolving, decoloring, filtering and ultrafiltering the sodium gluconate generated after centrifugation to obtain a purified sodium gluconate solution;
step S4: preparation of gluconic acid solution
Introducing the sodium gluconate solution purified in the step S3 into a continuous ion exchange system filled with strong acid cation resin to convert the sodium gluconate solution into a gluconic acid solution, and simultaneously storing sodium sulfate wastewater generated after the exchange of the strong acid cation resin is subjected to sulfuric acid regeneration treatment for later use;
step S5: preparation of gluconolactone wet product
Concentrating and crystallizing the gluconic acid solution prepared in the step S4 to obtain a glucolactone wet product;
step S6: preparation of finished product of gluconolactone
Firstly, centrifuging the gluconolactone wet product prepared in the step S5, and storing the waste water containing part of the gluconolactone generated after centrifugation for later use; then, carrying out vacuum drying and sieving treatment on the gluconolactone generated after centrifugation, and adding an anticaking agent to obtain a finished product of the gluconolactone;
step S7: waste water recovery and utilization
And (3) recycling the wastewater containing part of the sodium gluconate generated in the step S3, the sodium sulfate wastewater generated in the step S4 and the wastewater containing part of the gluconolactone generated in the step S6 in a centralized manner, and mixing the three types of wastewater to prepare the aliphatic water reducer mother liquor and the polycarboxylic acid water reducer mother liquor by replacing a common water source.
By adopting the technical scheme, the method takes the waste water generated by the centrifugation of the sodium gluconate, the sodium sulfate waste water generated after the regeneration of the resin and the waste water generated by the centrifugation of the gluconolactone as the water for producing the mother liquor of the aliphatic water reducing agent and the mother liquor of the polycarboxylic acid water reducing agent, and can replace part of raw and auxiliary materials of the water reducing agent, so that the zero discharge of the waste water generated in the process of producing the gluconolactone by adopting the sodium salt method is realized, the comprehensive treatment cost of the sewage of enterprises is greatly reduced, and the zero pollution to the environment is realized.
The working principle and advantages of the continuous ion exchange system are as follows:
sodium gluconate passes through a continuous ion exchange system filled with strong acid cation resin, sodium ions and hydrogen ions on the resin are exchanged in a resin tank, the effluent is the gluconic acid aqueous solution converted from the target product sodium gluconate, the exchanged resin enters a regeneration area along with the rotation of the system and is subjected to regeneration treatment of sulfuric acid in the regeneration area, and the converted resin enters the exchange area again to continuously replace the sodium ions in the sodium gluconate solution.
The continuous ion exchange system has shortened residence time and waiting time in the resin process, raised resin efficiency, capacity of reaching the operation effect similar to that of fixed bed with great amount of resin, capacity of regenerating deactivated resin timely to avoid long soaking and pollution and long service life of the resin.
The aliphatic water reducing agent is an anionic high molecular surfactant prepared by sulfonating and condensing acetone, formaldehyde, sodium sulfite and the like serving as main raw materials. The reaction mechanism of the aliphatic water reducing agent is relatively complex; although different processes and formulas can produce the aliphatic water reducing agent, the comprehensive properties of various products are greatly different.
Compared with the traditional water reducing agent, the polycarboxylic acid water reducing agent has many characteristics: 1. in the synthesis process, the polycarboxylic acid high-performance water reducing agent is synthesized by copolymerization of unsaturated monomers instead of polycondensation used by the traditional water reducing agent, so that the synthetic raw materials of the water reducing agent are more. 2. In terms of molecular structure, the molecular structure of the polycarboxylic acid high-performance water reducing agent is a linear comb-shaped structure, rather than a single linear structure of the traditional water reducing agent. The main chain of the water reducing agent is polymerized with a plurality of different active groups, such as carboxylic acid group (COOH), hydroxyl group (OH), sulfonic group (SO 3Na) and the like, SO that an electrostatic repulsion effect can be generated; the side chain of the compound has hydrophilic nonpolar active groups, and has higher steric hindrance effect. The water reducer has the advantages that the water reducer is incomparable due to wide raw material sources and unique molecular structure, and also does not use formaldehyde in the synthesis process, and belongs to a green and environment-friendly product, so the water reducer becomes one of the key points and hot points in the field of concrete admixture research.
As shown in figure 2 of the drawings, in which,
the first embodiment is as follows:
the preparation method of the mother liquor of the aliphatic water reducing agent comprises the following steps:
firstly, respectively adding 450Kg of wastewater and 140Kg of sodium sulfite solid in the step S7 into a reaction kettle for stirring and dissolving according to the stirring amount of each ton of materials;
secondly, respectively putting 260Kg of formaldehyde and 100Kg of acetone into a reaction kettle, and stirring for reaction to prepare an aliphatic water reducer mother solution;
wherein, the acetone which is partially volatilized during stirring is condensed and recycled to the reaction kettle for reuse.
Example two:
the preparation method of the mother liquor of the aliphatic water reducing agent comprises the following steps:
one is that 475Kg of the wastewater and 152.5Kg of the sodium sulfite solid in the step S7 are respectively put into a reaction kettle to be stirred and dissolved according to the stirring calculation of each ton of the materials;
secondly, 272.5Kg of formaldehyde and 107.5Kg of acetone are respectively put into a reaction kettle to be stirred and reacted to prepare mother liquor of the aliphatic water reducing agent;
wherein, the acetone which is partially volatilized during stirring is condensed and recycled to the reaction kettle for reuse.
Example three:
the preparation method of the mother liquor of the aliphatic water reducing agent comprises the following steps:
one is that according to the calculation of each ton of mixed materials, 500Kg of wastewater and 165Kg of sodium sulfite solid in the step S7 are respectively put into a reaction kettle for stirring and dissolving treatment;
secondly, respectively putting 285Kg of formaldehyde and 115Kg of acetone into a reaction kettle to carry out stirring reaction to prepare mother liquor of the aliphatic water reducer;
wherein, the acetone which is partially volatilized during stirring is condensed and recycled to the reaction kettle for reuse.
As shown in figure 3 of the drawings,
example four:
the preparation method of the polycarboxylate superplasticizer mother liquor comprises the following steps:
firstly, according to the calculation of each ton of mixed materials, 200Kg of wastewater, 1.5Kg of mercaptopropionic acid and 0.7Kg of food-grade vitamin in the step S7 are respectively put into a first reaction kettle to be stirred and mixed to form material A;
secondly, 150Kg of wastewater, 10Kg of acrylic acid and 35Kg of hydroxyethyl acrylate in the step S7 are respectively put into a second reaction kettle to be stirred and mixed to form a material B;
and thirdly, respectively putting 150Kg of the wastewater and 330Kg of unsaturated monomer in the step S7 into a third reaction kettle for stirring and dissolving, adding 5Kg of hydrogen peroxide for catalytic reaction, and then respectively adding the material A and the material B into the third reaction kettle for stirring and reacting to prepare the polycarboxylic acid water reducer mother liquor.
Example five:
the preparation method of the polycarboxylate superplasticizer mother liquor comprises the following steps:
firstly, according to the calculation of each ton of mixed materials, respectively putting 210Kg of wastewater, 1.65Kg of mercaptopropionic acid and 0.95Kg of food-grade vitamin C in the step S7 into a first reaction kettle, and stirring and mixing to form a material A;
secondly, respectively putting 165Kg of wastewater, 12.5Kg of acrylic acid and 40Kg of hydroxyethyl acrylate in the step S7 into a second reaction kettle, and stirring and mixing to form a material B;
and thirdly, respectively putting 175Kg of the wastewater and 345Kg of the unsaturated monomer in the step S7 into a third reaction kettle for stirring and dissolving, adding 7.5Kg of hydrogen peroxide for catalytic reaction, and then respectively adding the material A and the material B into the third reaction kettle in a dropwise manner for stirring and reacting to prepare the polycarboxylic acid water reducer mother liquor.
Example six:
the preparation method of the polycarboxylate superplasticizer mother liquor comprises the following steps:
firstly, according to the calculation of each ton of mixed materials, respectively putting 220Kg of wastewater, 1.8Kg of mercaptopropionic acid and 1.2Kg of food-grade vitamin in the step S7 into a first reaction kettle, and stirring and mixing to form a material A;
secondly, respectively putting 180Kg of wastewater, 15Kg of acrylic acid and 45Kg of hydroxyethyl acrylate in the step S7 into a second reaction kettle, and stirring and mixing to form a material B;
and thirdly, respectively putting 200Kg of the wastewater and 360Kg of unsaturated monomer in the step S7 into a third reaction kettle for stirring and dissolving, adding 8Kg of hydrogen peroxide for catalytic reaction, and then respectively adding the material A and the material B into the third reaction kettle for stirring and reacting to prepare the polycarboxylic acid water reducer mother liquor.
Example seven:
the preparation method of the polycarboxylate superplasticizer mother liquor comprises the following steps:
firstly, according to the calculation of each ton of mixed materials, 200Kg of wastewater, 1.8Kg of mercaptoethanol and 0.7Kg of food-grade vitamin in the step S7 are respectively put into a first reaction kettle to be stirred and mixed to form material A;
secondly, 150Kg of wastewater and 38Kg of acrylic acid in the step S7 are respectively put into a second reaction kettle to be stirred and mixed to form a material B;
and thirdly, respectively putting 150Kg of the wastewater and 330Kg of unsaturated monomer in the step S7 into a third reaction kettle for stirring and dissolving, adding 5Kg of hydrogen peroxide for catalytic reaction, and then respectively adding the material A and the material B into the third reaction kettle for stirring and reacting to prepare the polycarboxylic acid water reducer mother liquor.
Example eight:
the preparation method of the polycarboxylate superplasticizer mother liquor comprises the following steps:
firstly, according to the calculation of each ton of mixed materials, respectively putting 210Kg of wastewater, 2.15Kg of mercaptoethanol and 0.95Kg of food-grade vitamin C in the step S7 into a first reaction kettle, and stirring and mixing to form a material A;
secondly, respectively putting 165Kg of wastewater and 41.5Kg of acrylic acid in the step S7 into a second reaction kettle, and stirring and mixing to form a material B;
and thirdly, respectively putting 175Kg of the wastewater and 345Kg of the unsaturated monomer in the step S7 into a third reaction kettle for stirring and dissolving, adding 7.5Kg of hydrogen peroxide for catalytic reaction, and then respectively adding the material A and the material B into the third reaction kettle in a dropwise manner for stirring and reacting to prepare the polycarboxylic acid water reducer mother liquor.
Example nine:
the preparation method of the polycarboxylate superplasticizer mother liquor comprises the following steps:
firstly, according to the calculation of each ton of mixed materials, respectively putting 220Kg of wastewater, 2.5Kg of mercaptoethanol and 1.2Kg of food-grade vitamin in the step S7 into a first reaction kettle, and stirring and mixing to form a material A;
secondly, respectively putting 180Kg of wastewater and 45Kg of acrylic acid in the step S7 into a second reaction kettle, and stirring and mixing to form a material B;
and thirdly, respectively putting 200Kg of the wastewater and 360Kg of unsaturated monomer in the step S7 into a third reaction kettle for stirring and dissolving, adding 8Kg of hydrogen peroxide for catalytic reaction, and then respectively adding the material A and the material B into the third reaction kettle for stirring and reacting to prepare the polycarboxylic acid water reducer mother liquor.
In the first to ninth embodiments, the unsaturated monomer is any one of methallyl polyoxyethylene ether and prenol polyoxyethylene ether.
As shown in fig. 2 and 3, in the first to ninth embodiments, the mother liquid of the aliphatic water reducing agent and the mother liquid of the polycarboxylic acid water reducing agent are respectively compounded by adding white sugar, an air entraining agent, a defoaming agent, the mother liquid of sodium gluconate and the wastewater in the step S7 according to the concrete strength and the seasonal construction requirements to form a finished product of the aliphatic water reducing agent and a finished product of the polycarboxylic acid water reducing agent.
By adopting the technical scheme, the wastewater is divided into three types: wastewater containing sodium gluconate, sodium sulfate wastewater and wastewater containing gluconolactone;
firstly, the three kinds of waste water can be used as water for producing mother liquor of the aliphatic water reducing agent and mother liquor of the polycarboxylic acid water reducing agent; secondly, the sodium sulfate in the sodium sulfate wastewater is very stable, the synthetic reaction of the water reducing agent cannot be influenced, and the sodium sulfate can be used as an early strength agent for compounding in the later period, so that the use cost of the early strength agent is reduced; and thirdly, the wastewater containing the sodium gluconate and the wastewater containing the gluconolactone can replace part of raw and auxiliary materials of the water reducing agent, and can play a role in retarding coagulation, so that the dosage cost of the sodium gluconate mother liquor during later-stage compounding is reduced.
Sodium sulfate is a main raw material of the early strength agent in China and is also an important component of the composite early strength agent. The sodium sulfate reacts with calcium hydroxide generated by cement hydration in the cement concrete to generate sodium hydroxide and calcium sulfate. The calcium sulfate has fine particles and higher activity than gypsum, and can quickly react with tricalcium aluminate to generate hydrated calcium sulphoaluminate, and the sodium hydroxide can accelerate the reaction, and the hydrated calcium sulphoaluminate is the key for promoting the early strength of cement concrete. However, this reaction must be carried out at an appropriate amount to ensure that it occurs before hardening, and if the amount is too large, the reaction continues after hardening, which leads to cracking of the cement concrete, a reduction in strength and durability, and a serious loss in dynamic load characteristics, because it continues to expand. Therefore, the mixing amount of the sodium sulfate in the dry environment is not more than 2 percent; when the retarder is doped, the setting and hardening time of cement concrete is delayed, the hydrated calcium sulphoaluminate has longer reaction generation time and is in a plasticity stage, so that harmful internal stress is avoided, and simultaneously, when the retarder is doped, the doping amount of sodium sulfate can be increased to 3 percent at most in a dry environment; in order to ensure that the autogenous internal stress of the cement concrete caused by the hydrated calcium sulphoaluminate is not too large, the mixing amount of the sodium sulfate of the prestressed concrete is not more than 1 percent. Sodium sulfate has no corrosion effect on the steel bar; the proper mixing amount is 0.5-2%, and the early strength agent can accelerate the hardening process of concrete and is mainly used for winter construction and rush repair engineering. The early strength agent can make the concrete have the form removal strength in a short time, and accelerate the turnover rate of the form.
The role of sodium gluconate in concrete: 1. with sodium gluconate, the w/c ratio (water-cement ratio of the concrete) can be reduced, which can increase the strength of the concrete, which is a good type of concrete. 2. Large blocks and heavy weight of the pouring work are difficult to construct. The addition of sodium gluconate can improve the workability of concrete and delay the setting time, so as to avoid the formation of contact surface on the structure, and improve the structural strength. 3. It is important to improve workability by keeping the w/c ratio constant in hot areas. Large amounts of sodium gluconate have been used in middle east bridge construction. 4. The addition of sodium gluconate to concrete mixture can delay the setting time, which is important for long-term and high-difficulty pouring. 5. In the modern concrete industry, where ready-mixed concrete is prepared at a central location and shipped by truck mixer, it is important to increase workability and initial set time. 6. The concrete with higher strength and durability can be prepared by reducing the w/c ratio, and the purpose can be achieved by the sodium gluconate. This is important for high strength reinforced concrete. 7. The prefabricated masonry mortar must be usable for a long time. The working period can be prolonged by adding sodium gluconate. 8. The oil well irrigation slurry is difficult to operate due to high temperature, and the concrete can work for several hours at the temperature of 170 ℃ after the sodium gluconate is added.
As shown in fig. 1, the rice residue generated in the step S1 is cleaned and dried to prepare rice protein powder, and the rice residue wastewater generated during cleaning replaces part of the antifoaming agent and is added into the compounding of the finished water reducing agent.
By adopting the technical scheme, the use of the defoaming agent in the compounding process of the finished water reducing agent can be reduced, and the cost is saved.
As shown in fig. 1, the anticaking agent in step S6 is silicon dioxide powder with a particle size of 1500 meshes or more.
As shown in fig. 1 and 4, the preparation of the gluconic acid solution in the step S4 may be performed by introducing the gluconic acid solution into a membrane treatment system, and directly converting the bulk-purified sodium gluconate solution in the step S3 into a gluconic acid solution and a sodium hydroxide solution by using a bipolar membrane electrodialysis method; and concentrating and crystallizing the gluconic acid solution to obtain a finished product of glucolactone, concentrating the sodium hydroxide solution, and putting the concentrated sodium hydroxide solution into the step S2 to react to generate the sodium gluconate solution.
By adopting the technical scheme, the gluconolactone can achieve clean production without wastewater. According to the measurement and calculation, about 3 tons of 8 percent sodium hydroxide solution is produced every ton of gluconic acid is produced, and the sodium hydroxide solution is concentrated to 20 percent by electrodialysis and can be directly reused for producing the sodium gluconate.
The bipolar membrane is an ion exchange membrane with special function, and the middle layer of the bipolar membrane is subjected to water dissociation under the action of an electric field to generate H+And OH-Ions. The bipolar membrane electrodialysis technology is to combine the special function into common electrodialysis, so that the instant acid/alkali production/regeneration, or acidification and/or alkalization can be realized. The technology can be widely applied to the fields of food processing, chemical synthesis, environmental protection and the like, and the bipolar membrane electrodialysis technology is praised as a sustainable development technology due to the technical advancement, economic competitiveness and environmental friendliness. The bipolar membrane electrodialysis technology is applied to the production/regeneration process of traditional organic acid or organic base, so that the conversion of organic acid salt or organic base salt can be realized, and the generated NaOH or HCl can be reused in the generation process.
The aliphatic water reducer mother liquor and the polycarboxylate water reducer mother liquor prepared in the first to ninth embodiments are subjected to the execution standard GB8076-2008, and standard cement is used, and the obtained test item data are respectively shown in the following tables I and II:
table one:
table two:
according to the data in the table I and the table II, the wastewater generated in the process of producing the gluconolactone by the sodium salt method is used for preparing the aliphatic water reducer mother liquor and the polycarboxylate water reducer mother liquor, and the two water reducer mother liquors both reach the quality qualified standard.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. The environment-friendly glucolactone processing method is characterized by comprising the following steps:
step S1: preparation of glucose solution
Firstly, introducing running water into starch to generate starch milk or introducing running water into rice to grind the rice into rice milk, secondly, adding amylase into the starch milk or the rice milk to adjust the milk and liquefy and preserve heat, then, carrying out rice residue removal treatment through solid-liquid separation, and adding saccharifying enzyme into the liquid after removing the residues to saccharify the liquid to generate glucose solution;
step S2: preparation of sodium gluconate solution
Adding glucose oxidase into the glucose solution prepared in the step S1, introducing oxygen into the glucose solution for fermentation treatment, and adding sodium hydroxide after fermentation to react to generate a sodium gluconate solution;
step S3: purification of sodium gluconate solution
Firstly, sequentially filtering, concentrating, crystallizing and centrifuging the sodium gluconate solution prepared in the step S2, and storing the waste water containing part of sodium gluconate generated after centrifugation for later use; then, sequentially dissolving, decoloring, filtering and ultrafiltering the sodium gluconate generated after centrifugation to obtain a purified sodium gluconate solution;
step S4: preparation of gluconic acid solution
Introducing the sodium gluconate solution purified in the step S3 into a continuous ion exchange system filled with strong acid cation resin to convert the sodium gluconate solution into a gluconic acid solution, and simultaneously storing sodium sulfate wastewater generated after the exchange of the strong acid cation resin is subjected to sulfuric acid regeneration treatment for later use;
step S5: preparation of gluconolactone wet product
Concentrating and crystallizing the gluconic acid solution prepared in the step S4 to obtain a glucolactone wet product;
step S6: preparation of finished product of gluconolactone
Firstly, centrifuging the gluconolactone wet product prepared in the step S5, and storing the waste water containing part of the gluconolactone generated after centrifugation for later use; then, carrying out vacuum drying and sieving treatment on the gluconolactone generated after centrifugation, and adding an anticaking agent to obtain a finished product of the gluconolactone;
step S7: waste water recovery and utilization
And (3) recycling the wastewater containing part of the sodium gluconate generated in the step S3, the sodium sulfate wastewater generated in the step S4 and the wastewater containing part of the gluconolactone generated in the step S6 in a centralized manner, and mixing the three types of wastewater to prepare the aliphatic water reducer mother liquor and the polycarboxylic acid water reducer mother liquor by replacing a common water source.
2. The environment-friendly glucolactone processing method according to claim 1, characterized in that the preparation method of the aliphatic water reducer mother liquor comprises the following steps:
firstly, respectively putting 45-50% of the wastewater and 14-16.5% of sodium sulfite solid in the step S7 into a reaction kettle according to the mass percentage for stirring and dissolving treatment;
secondly, according to the mass percentage, 26-28.5 percent of formaldehyde and 10-11.5 percent of acetone are respectively put into a reaction kettle to be stirred and reacted to prepare mother liquor of the aliphatic water reducing agent;
wherein, the acetone which is partially volatilized during stirring is condensed and recycled to the reaction kettle for reuse.
3. The environment-friendly glucolactone processing method according to claim 1, characterized in that the preparation method of the polycarboxylate superplasticizer mother liquor comprises the following steps:
firstly, according to the mass percentage, 20 to 22 percent of the waste water, 0.15 to 0.18 percent of mercaptopropionic acid and 0.07 to 0.12 percent of food-grade vitamin C in the step S7 are respectively put into a first reaction kettle, and stirred and mixed to form material A, or 20 to 22 percent of the waste water, 0.18 to 0.25 percent of mercaptoethanol and 0.07 to 0.12 percent of food-grade vitamin C;
secondly, according to the mass percentage, 15 to 18 percent of the waste water, 3.8 to 4.5 percent of the acrylic acid, or 15 to 18 percent of the waste water, 1 to 1.5 percent of the acrylic acid and 3.5 to 4.5 percent of the hydroxyethyl acrylate in the step S7 are respectively put into a second reaction kettle to be stirred and mixed to form a material B;
and thirdly, respectively putting 15-20% of the wastewater and 33-36% of unsaturated monomers in the step S7 into a third reaction kettle according to the mass percentage, stirring and dissolving, adding 0.5-0.8% of hydrogen peroxide for catalytic reaction, and then respectively adding the material A and the material B into the third reaction kettle in a dropwise manner for stirring reaction to prepare the polycarboxylic acid water reducer mother liquor.
4. The method for processing environmentally friendly gluconolactone according to claim 3, wherein: the unsaturated monomer is any one of methyl allyl polyoxyethylene ether or prenol polyoxyethylene ether.
5. The environmentally friendly gluconolactone processing method according to any one of claims 2 or 3, wherein: and (3) adding white sugar, an air entraining agent, a defoaming agent, sodium gluconate mother liquor and the wastewater in the step S7 into the aliphatic water reducer mother liquor and the polycarboxylate water reducer mother liquor respectively, and compounding according to the concrete strength and seasonal construction requirements to form an aliphatic water reducer finished product and a polycarboxylate water reducer finished product.
6. The method for processing environmentally friendly gluconolactone according to claim 5, wherein: and (5) cleaning and drying the rice residue generated in the step (S1) to prepare rice protein powder, and putting the rice residue wastewater generated in the cleaning process into the compounding of the finished water reducing agent instead of a part of defoaming agent.
7. The method for processing environmentally friendly gluconolactone according to claim 1, wherein: the anticaking agent in step S6 is a silica powder having a particle size of 1500 meshes or more.
8. The method for processing environmentally friendly gluconolactone according to claim 1, wherein: the preparation of the gluconic acid solution in the step S4 can also be conducted to a membrane treatment system, and the sodium gluconate solution after the volume purification in the step S3 is directly converted into the gluconic acid solution and the sodium hydroxide solution by using a bipolar membrane electrodialysis method; and concentrating and crystallizing the gluconic acid solution to obtain a finished product of glucolactone, concentrating the sodium hydroxide solution, and putting the concentrated sodium hydroxide solution into the step S2 to react to generate the sodium gluconate solution.
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| CN101607952A (en) * | 2009-07-14 | 2009-12-23 | 浙江天益食品添加剂有限公司 | A kind of preparation method of maltonic acid-delta-lactone |
| CN101671324A (en) * | 2009-09-24 | 2010-03-17 | 厦门世达膜科技有限公司 | Production method of glucolactone |
| CN102992680A (en) * | 2012-08-21 | 2013-03-27 | 江苏百瑞吉新材料有限公司 | Method for preparing aliphatic water reducer without heating |
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| CN107475322A (en) * | 2017-07-25 | 2017-12-15 | 安徽万德生物科技有限公司 | A kind of technique for preparing fructose syrup |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101607952A (en) * | 2009-07-14 | 2009-12-23 | 浙江天益食品添加剂有限公司 | A kind of preparation method of maltonic acid-delta-lactone |
| CN101671324A (en) * | 2009-09-24 | 2010-03-17 | 厦门世达膜科技有限公司 | Production method of glucolactone |
| CN102992680A (en) * | 2012-08-21 | 2013-03-27 | 江苏百瑞吉新材料有限公司 | Method for preparing aliphatic water reducer without heating |
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Address after: 242000 Taocheng Town Industrial Zone, Langxi County, Xuancheng City, Anhui Province Applicant after: Anhui Xingzhou Pharmaceutical Co.,Ltd. Address before: 242000 Taocheng Town Industrial Zone, Langxi County, Xuancheng City, Anhui Province Applicant before: ANHUI XINGZHOU MEDICINE FOOD Co.,Ltd. |