CN113003898A - Corn soaking water treatment method - Google Patents
Corn soaking water treatment method Download PDFInfo
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- CN113003898A CN113003898A CN202110444888.8A CN202110444888A CN113003898A CN 113003898 A CN113003898 A CN 113003898A CN 202110444888 A CN202110444888 A CN 202110444888A CN 113003898 A CN113003898 A CN 113003898A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 240000008042 Zea mays Species 0.000 title claims abstract description 57
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 title claims abstract description 57
- 235000002017 Zea mays subsp mays Nutrition 0.000 title claims abstract description 57
- 235000005822 corn Nutrition 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000011282 treatment Methods 0.000 title claims abstract description 41
- 238000002791 soaking Methods 0.000 title claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 95
- 229920005989 resin Polymers 0.000 claims abstract description 95
- 239000012528 membrane Substances 0.000 claims abstract description 28
- 150000001450 anions Chemical class 0.000 claims abstract description 24
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 21
- 125000002091 cationic group Chemical group 0.000 claims abstract description 21
- 238000001728 nano-filtration Methods 0.000 claims abstract description 21
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 21
- 239000012466 permeate Substances 0.000 claims abstract description 20
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 20
- 239000012530 fluid Substances 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000006228 supernatant Substances 0.000 claims abstract description 11
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 28
- 150000001768 cations Chemical class 0.000 claims description 24
- 239000004310 lactic acid Substances 0.000 claims description 14
- 235000014655 lactic acid Nutrition 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 102000004169 proteins and genes Human genes 0.000 claims description 11
- 108090000623 proteins and genes Proteins 0.000 claims description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 10
- 238000000855 fermentation Methods 0.000 claims description 10
- 230000004151 fermentation Effects 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000011591 potassium Substances 0.000 claims description 10
- 238000001223 reverse osmosis Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 239000003957 anion exchange resin Substances 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 abstract description 26
- 239000001103 potassium chloride Substances 0.000 abstract description 13
- 235000011164 potassium chloride Nutrition 0.000 abstract description 13
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 abstract description 12
- 229940068041 phytic acid Drugs 0.000 abstract description 12
- 239000000467 phytic acid Substances 0.000 abstract description 12
- 239000002351 wastewater Substances 0.000 abstract description 7
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 20
- 238000004821 distillation Methods 0.000 description 15
- 235000018102 proteins Nutrition 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002068 microbial inoculum Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000012465 retentate Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 235000019750 Crude protein Nutrition 0.000 description 2
- SQUHHTBVTRBESD-UHFFFAOYSA-N Hexa-Ac-myo-Inositol Natural products CC(=O)OC1C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O SQUHHTBVTRBESD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 description 2
- 229960000367 inositol Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 2
- 229930195730 Aflatoxin Natural products 0.000 description 1
- XWIYFDMXXLINPU-UHFFFAOYSA-N Aflatoxin G Chemical compound O=C1OCCC2=C1C(=O)OC1=C2C(OC)=CC2=C1C1C=COC1O2 XWIYFDMXXLINPU-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000005409 aflatoxin Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 235000004252 protein component Nutrition 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QHDCFDQKXQIXLF-UHFFFAOYSA-N sulfuric acid sulfurous acid Chemical compound OS(O)=O.OS(O)(=O)=O QHDCFDQKXQIXLF-UHFFFAOYSA-N 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/117—Esters of phosphoric acids with cycloaliphatic alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/14—Extraction; Separation; Purification
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/10—Treatment of water, waste water, or sewage by heating by distillation or evaporation by direct contact with a particulate solid or with a fluid, as a heat transfer medium
- C02F1/12—Spray evaporation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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Abstract
The invention relates to the technical field of corn soaking water treatment, in particular to a corn soaking water treatment method, which comprises the following steps: (1) enabling the supernatant after the corn is soaked in the water and kept stand to enter a cationic resin column, and collecting a first effluent and a second effluent; (2) the first effluent enters an anion resin column, the third effluent is collected, the second effluent enters the anion resin column, and the first section effluent with the pH value of 3.3 to neutral and the second section effluent with the pH value of less than 3.3 are respectively collected; (3) the first-stage effluent liquid is treated by ultrafiltration and nanofiltration, and trapped fluid is collected; (4) filtering the third effluent collected in the step (2), fermenting the collected trapped fluid, and filtering the collected permeate through a nanofiltration membrane; by the treatment method, potassium ions in the corn soaking water can be recycled, the discharge amount of wastewater is reduced, and the consumption of potassium chloride raw materials for desorbing phytic acid is reduced.
Description
Technical Field
The invention relates to the technical field of corn soaking water treatment, in particular to a corn soaking water treatment method.
Background
In the corn starch wet milling method production process, corn soaking water is used as main production wastewater, wherein the solid content is about 10-12%, and the corn soaking water contains substances such as 5-6% of protein, 2-3% of lactic acid, 1% of phytic acid, 1% of sugar, a small amount of starch residue, inorganic salt and the like, and the conventional treatment modes of the corn soaking water at present mainly comprise the following two modes: (1) the corn steep water is evaporated and concentrated from 6 to 10 percent to 40 percent of corn steep liquor through a multi-effect evaporator, the corn steep liquor is directly sold or sprayed and sold, but the price of the corn steep liquor is greatly fluctuated due to the influence of seasons or purchasers, and the treatment cost of high COD sewage exists; (2) the corn soaking water is used for producing the protein powder, but the corn soaking water contains protein components, small molecular sugar, (sulfite) sulfate, pigment and the like, and even aflatoxin due to complex components, and is directly used for producing the protein powder, so that the product has poor quality and has food or other safety risks; (3) in order to effectively utilize components in the corn soaking water, the prior treatment process adopts a process method of treating the corn soaking water to obtain products such as inositol, protein, lactic acid and the like; when the phytic acid is desorbed, newly prepared potassium chloride solution is used as a desorbent, and the corn soaking water contains potassium ions, but the potassium ions are not recycled by the conventional process method, so that the resource waste is caused, and in addition, the operation process for preparing the lactic acid is complicated, the cost is high, and the wastewater is easily generated. Therefore, in order to solve the above problems, there is a need to establish a method for treating corn steep water.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the defects in the prior art, the method for treating the corn soaking water is provided, potassium ions in the corn soaking water can be recycled by the method, the discharge amount of wastewater is reduced, and the consumption of a potassium chloride raw material for desorbing phytic acid is reduced.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a corn steep water treatment method comprises the following steps:
(1) allowing the supernatant of the corn soaking water after standing to enter a cation resin column, collecting a first effluent for later use, washing the cation resin column with hydrochloric acid, and collecting a second effluent for later use;
(2) enabling the first effluent obtained in the step (1) to enter an anion resin column, collecting a third effluent for later use, enabling the second effluent obtained in the step (1) to serve as a desorbent to enter the anion resin column, and respectively collecting a first-stage effluent with the pH value of 3.3 to neutral and a second-stage effluent with the pH value of less than 3.3;
(3) performing ultrafiltration and nanofiltration treatment on the first-stage effluent collected in the step (2), wherein the collected trapped fluid is a potassium phytate solution; taking the second-stage effluent collected in the step (2) as a desorbent of the next batch of the cationic resin column, and introducing the second-stage effluent into the cationic resin column, wherein the collected effluent is used as a desorbent component of the next batch of the anionic resin column in the step (2);
(4) filtering the third effluent collected in the step (2) by using an ultrafiltration membrane, fermenting the collected trapped fluid, filtering the collected permeate by using a nanofiltration membrane, and respectively collecting the trapped fluid and the permeate for later use;
(5) spray drying the trapped fluid for later use in the step (4) to obtain a corn protein powder product; treating the reserved permeate with a reverse osmosis membrane, and respectively collecting the trapped fluid and the permeate for later use;
(6) carrying out vacuum concentration and vacuum distillation treatment on the trapped liquid collected in the step (5) to obtain a lactic acid product; and (4) mechanically applying the permeate collected in the step (5) as process production water.
As an improved technical scheme, the resin in the cation resin column in the step (1) is strong acid cation resin, the type of the resin is Hairun HAD-10 resin, and the volume of the resin in the cation resin column is 3 BV.
As an improved technical scheme, the concentration of the hydrochloric acid in the step (1) is 8-10% w/v, the volume of the hydrochloric acid is 1.3-2 times of the volume of the resin in the cationic resin column, and the hydrochloric acid enters the cationic resin column at the flow rate of 0.5 BV/h.
As an improved technical scheme, the resin in the anion resin column in the step (2) is a weak base anion exchange resin, and the type of the resin is weak base acrylic resin ZG 312.
As an improved technical scheme, fermentation strains are added when the trapped fluid collected in the step (4) is fermented, the mixture is stirred for 10-15min every 3h, the fermentation temperature is maintained at 30-50 ℃, and the mixture is fermented and stirred for 7-10 days.
As an improved technical scheme, the molecular weight cut-off of the ultrafiltration membrane is 10-20 ten thousand, the molecular weight cut-off of the nanofiltration membrane is 500-600, and the molecular weight cut-off of the reverse osmosis membrane is less than 100.
As an improved technical scheme, the corn soaking water in the step (1) is kept stand for 4-6h at the temperature of 45-50 ℃.
After the technical scheme is adopted, the invention has the beneficial effects that:
the treatment method comprises the steps of adsorbing supernate obtained after standing corn soaking water through a cation resin column, desorbing the cation resin column through hydrochloric acid, enabling the obtained potassium chloride and hydrochloric acid mixed solution to enter an anion resin column for desorbing phytic acid, respectively collecting a first-stage effluent liquid with the pH value of 3.3 to neutral and a second-stage effluent liquid with the pH value of less than 3.3, and collecting trapped liquid of the first-stage effluent liquid through ultrafiltration and nanofiltration treatment to be a potassium phytate solution; the effluent liquid of the second section is used as the desorbent component of the next batch of the cation resin column again, and the collected effluent liquid is used as the desorbent component of the next batch of the anion resin column; the process method realizes the recycling of potassium ions in the corn soaking water, greatly reduces the consumption of potassium chloride for desorbing the phytic acid, has simple operation in the whole process, does not need other operations such as membrane filtration on the effluent liquid after the desorption of the cation resin column, and does not need regeneration treatment on the cation resin column by alkali liquor; the treatment method of the invention intercepts and ferments the crude protein in the corn soaking water, and the crude protein is sold as a product; the treatment method of the invention recovers the lactic acid in the corn soaking water, adopts ultrafiltration, nanofiltration and reverse osmosis operation, and has simple and convenient operation; the treatment method comprises the steps of adsorbing the first effluent after the effluent passes through the cation resin column by the anion resin column, desorbing by using potassium chloride, and carrying out a series of treatments on the collected desorption solution to obtain inositol and high-value byproducts. The whole treatment method also recycles the wastewater, and saves water. The processing method fully utilizes the components of the corn soaking water, does not waste any resources, obtains a plurality of products, and greatly brings economic benefits to enterprises.
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 examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A corn soaking water treatment method comprises the following steps:
(1) standing 650L of supernatant of corn soaking water at 45-50 ℃ for 4h, feeding the supernatant into a 135L cationic resin column (strong acid type cationic resin sea-wet HAD-10, the volume of resin in the cationic resin column is 3BV) of resin filler in a countercurrent manner at the flow rate of 1.2BV/h, collecting a first effluent for later use, simultaneously washing the cationic resin column by 8% w/v and 180L hydrochloric acid solution according to 0.5BV/h, and collecting a second effluent for later use;
(2) enabling the first effluent obtained in the step (1) to enter an anion resin column (a filler in the resin column is gel-type weakly alkaline acrylic resin ZG312), collecting a third effluent for later use, enabling the third effluent to enter the anion resin column by taking the second effluent obtained in the step (1) as a desorbent, and respectively collecting 75L (a mixed solution of potassium phytate and potassium chloride) of a first-stage effluent with the pH value of 3.3 to neutral and 75L (a mixed solution of phytic acid and hydrochloric acid) of a second-stage effluent with the pH value of less than 3.3, and supplementing the first-stage effluent to 180L by using newly-prepared hydrochloric acid;
(3) the first-stage effluent collected in the step (2) is subjected to ultrafiltration (an ultrafiltration membrane with the molecular weight cutoff of 10-20 ten thousand) and nanofiltration treatment (a nanofiltration membrane with the molecular weight cutoff of 800-; taking the second-stage effluent collected in the step (2) as a desorbent of the next batch of the cation resin column, and introducing the second-stage effluent into the cation resin column, wherein the collected effluent is used as a desorbent component of the next batch of the anion resin column;
(4) filtering 650L of third effluent collected in the step (2) by an ultrafiltration membrane with the molecular weight cutoff of 10-20 ten thousand, fermenting 50L of collected retentate with the solid content of 18% w/v (the added strain is EM microbial inoculum, the addition amount is 0.05% w/v, the strain is purchased from manufacturers), stirring for 10-15min every 3h, maintaining the fermentation temperature at 30-50 ℃, fermenting and stirring for 7-10 days, wherein the organic matter content of the solid content of the obtained fermentation product reaches 40%, and the bacterial content reaches more than 5000/g. ) Filtering 600L of the collected permeation solution by a nanofiltration membrane with the molecular weight cutoff of 500, and respectively collecting the trapped solution and the permeation solution for later use;
(5) treating 120L of trapped fluid for later use in the step (4) until the solid content reaches 30% (w/v) by spray drying (the air inlet temperature is 130 ℃, the air outlet temperature is 95 ℃) to obtain a corn protein powder product; treating 480L of the reserved permeate through a reverse osmosis membrane (the molecular weight cut-off is less than 100), and respectively collecting the cut-off and the permeate for later use;
(6) allowing 240L of trapped liquid collected in the step (5) to enter a distillation still with the pressure of-0.09 to-0.095 Mpa, heating for distillation, separately collecting water with a low boiling point until no distillation, increasing the vacuum degree to be vacuum stable at 100Pa, heating for distillation, separately collecting about 200L of water with the temperature lower than 55 ℃, switching a fraction collection tank to collect fractions with the temperature of 82-85 ℃/100Pa, and distilling until no distillation, so as to obtain 22kg of lactic acid aqueous solution with the lactic acid content of 50%; adding 20L of water into the dry matter at the bottom of the kettle, heating, boiling, discharging, and drying to obtain 15 kg; and (4) mechanically applying 240L of permeate collected in the step (5) as process production water.
Example 2
A corn soaking water treatment method comprises the following steps:
(1) standing 650L of supernatant of corn soaking water at 45-50 ℃ for 5h, feeding the supernatant into a 135L cationic resin column (strong acid type cationic resin sea-wet HAD-10, the volume of resin in the cationic resin column is 3BV) of resin filler in a countercurrent manner at the flow rate of 1.2BV/h, collecting a first effluent for later use, simultaneously washing the cationic resin column by adopting 9% w/v and 180L hydrochloric acid solution according to 0.5BV/h, and collecting a second effluent for later use;
(2) allowing the first effluent collected in the step (1) to enter an anion resin column (the filler in the resin column is gel-type weakly basic acrylic resin ZG312), collecting a third effluent for later use, allowing the second effluent obtained in the step (1) to serve as a desorbent to enter the anion resin column, and respectively collecting a first-stage effluent (a mixed solution of potassium phytate and potassium chloride) with the pH value of 3.3 to neutral and a second-stage effluent (a mixed solution of phytic acid and hydrochloric acid) with the pH value of less than 3.3;
(3) performing ultrafiltration (ultrafiltration membrane with molecular weight cut-off of 10-20 ten thousand) and nanofiltration treatment (nanofiltration membrane with molecular weight cut-off of 800) on the first-stage effluent collected in the step (2), wherein the collected trapped liquid is 19L of potassium phytate solution (the content of potassium phytate is 26%); taking the second-stage effluent collected in the step (2) as a desorbent of the next batch of the cationic resin column, and introducing the second-stage effluent into the cationic resin column, wherein the collected effluent is used as a desorbent component of the next batch of the anionic resin column in the step (2);
(4) filtering 650L of third effluent collected in the step (2) by an ultrafiltration membrane with the molecular weight cutoff of 10-20 ten thousand, fermenting the collected 50L of retentate with the solid content of 18% w/v (the added strain is EM microbial inoculum with the addition of 0.05% w/v), stirring for 10-15min every 3h, maintaining the fermentation temperature at 30-50 ℃, and fermenting and stirring for 7-10 days, wherein the organic matter content of the solid content of the obtained fermentation product reaches 40%, and the bacterial content reaches more than 5000/g. ) Filtering 600L of the collected permeation solution by a nanofiltration membrane with the molecular weight cutoff of 500, and respectively collecting the trapped solution and the permeation solution for later use;
(5) treating 120L of trapped fluid for later use in the step (4) until the solid content reaches 30% (w/v) by spray drying (the air inlet temperature is 130 ℃, the air outlet temperature is 95 ℃) to obtain a corn protein powder product; treating 480L of the reserved permeate through a reverse osmosis membrane (the molecular weight cut-off is less than 100), and respectively collecting the cut-off and the permeate for later use;
(6) allowing 240L of trapped liquid collected in the step (5) to enter a distillation still with the pressure of-0.09 to-0.095 Mpa, heating for distillation, separately collecting water with a low boiling point until no distillation, increasing the vacuum degree to be vacuum stable at 100Pa, heating for distillation, separately collecting about 200L of water with the temperature lower than 55 ℃, switching a fraction collection tank to collect fractions with the temperature of 82-85 ℃/100Pa, and distilling until no distillation, so as to obtain 22kg of lactic acid aqueous solution with the lactic acid content of 50%; adding 20L of water into the dry matter at the bottom of the kettle, heating, boiling, discharging and drying to obtain 15 kg; and (4) mechanically applying 240L of permeate collected in the step (5) as process production water.
Example 3
A corn soaking water treatment method comprises the following steps:
(1) standing 650L of supernatant of corn soaking water at 45-50 ℃ for 6h, feeding the supernatant into a 135L cationic resin column (strong acid type cationic resin is Hai run on HAD-10, the volume of resin in the cationic resin column is 3BV) of resin filler in a countercurrent manner of 1.2BV/h, collecting a first effluent for later use, simultaneously washing the cationic resin column by 10% w/v and 180L of hydrochloric acid solution according to 0.5BV/h, and collecting a second effluent for later use;
(2) enabling the first effluent collected in the step (1) to enter an anion resin column (the filler in the resin column is gel type weakly alkaline acrylic resin ZG312, the volume of the anion resin column is 45L), collecting a third effluent for later use, enabling the second effluent in the step (1) to serve as a desorbent to enter the anion resin column, and respectively collecting a first-stage effluent (a mixed solution of potassium phytate and potassium chloride, the first 26L and the subsequent 75L) with the pH value of 3.3 to be neutral and a second-stage effluent (a mixed solution of phytic acid and hydrochloric acid, the first 154L and the subsequent 105L) with the pH value of less than 3.3;
(3) the first-stage effluent collected in the step (2) is subjected to ultrafiltration (an ultrafiltration membrane with the molecular weight cutoff of 10-20 ten thousand) and nanofiltration treatment (a nanofiltration membrane with the molecular weight cutoff of 800-; taking the second-stage effluent collected in the step (2) as a desorbent of the next batch of the cation resin column, and introducing the second-stage effluent into the cation resin column, wherein the collected effluent is used as a desorbent component of the next batch of the anion resin column;
(4) filtering 650L of third effluent collected in the step (3) by an ultrafiltration membrane with the molecular weight cutoff of 10-20 ten thousand, fermenting the collected 50L of retentate with the solid content of 18% w/v (the added strain is EM microbial inoculum with the addition of 0.05% w/v), stirring for 10-15min every 3h, maintaining the fermentation temperature at 30-50 ℃, and fermenting and stirring for 7-10 days, wherein the organic matter content of the solid content of the obtained fermentation product reaches 40%, and the bacterial content reaches more than 5000/g. ) Filtering 600L of the collected permeation solution by a nanofiltration membrane with the molecular weight cutoff of 500, and respectively collecting the trapped solution and the permeation solution for later use;
(5) treating 120L of trapped fluid for later use in the step (4) until the solid content reaches 30% (w/v) by spray drying (the air inlet temperature is 130 ℃, the air outlet temperature is 95 ℃) to obtain a corn protein powder product; treating 480L of the reserved permeate through a reverse osmosis membrane (the molecular weight cut-off is less than 100), and respectively collecting the cut-off and the permeate for later use;
(6) allowing 240L of trapped liquid collected in the step (5) to enter a distillation still with the pressure of-0.09 to-0.095 Mpa, heating for distillation, separately collecting water with a low boiling point until no distillation, increasing the vacuum degree to be vacuum stable at 100Pa, heating for distillation, separately collecting about 200L of water with the temperature lower than 55 ℃, collecting fractions at the temperature of 82-85 ℃/100Pa, and distilling until no distillation to obtain 22kg of lactic acid aqueous solution with the lactic acid content of 50%; adding 20L of water into the dry matter at the bottom of the kettle, heating, boiling, discharging and drying to obtain 15 kg; and (4) mechanically applying 240L of permeate collected in the step (5) as process production water.
To better demonstrate the advantages of the treatment method of the present invention over the prior art, the following 2 comparative examples are given, and the results of the specific experiments are given in table 1.
Comparative example 1
Different from the example 1, the supernatant fluid of the corn soaking water after standing is not absorbed by a cation resin column, but directly enters an anion resin column, the effluent liquid is subjected to ultrafiltration, nanofiltration and reverse osmosis (the treatment method is the same as the example 1), and the anion resin column is desorbed by potassium chloride solution (the treatment method is the same as the example 1);
comparative example 2
Different from the example 1, the supernatant fluid of the corn soaking water after standing is not absorbed by a cation resin column, but directly enters an anion resin column, the effluent liquid is subjected to ultrafiltration and nanofiltration operation (the treatment mode is the same as the example 1), and the anion resin column is desorbed by potassium chloride solution (the treatment mode is the same as the example 1);
TABLE 1
The data in table 1 show that the process method provided by the invention realizes the recycling of potassium in the corn soaking water, the potassium chloride raw material is not consumed during the desorption of phytic acid in the examples 1 to 3, the zero discharge of wastewater is realized in the whole process, the consumption of the potassium chloride raw material is greatly reduced compared with the comparative examples 1 and 2, the resource waste is avoided, and the zero discharge of wastewater is also realized.
Here, it should be noted that the data in Table 1 are the data in Table 1 obtained by calculating that the phytic acid in 1000L of the corn steep water contains 13.59kg of potassium phytate 10.1kg, 52kg of protein and 23.9kg of lactic acid according to the measurement of the corn steep water containing 10.8% w/v of protein, 5.2% w/v of lactic acid and 1.01% w/v of phytic acid in the corn steep water of the batch.
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 (7)
1. A corn soaking water treatment method is characterized by comprising the following steps:
(1) allowing the supernatant of the corn soaking water after standing to enter a cation resin column, collecting a first effluent for later use, washing the cation resin column with hydrochloric acid, and collecting a second effluent for later use;
(2) enabling the first effluent obtained in the step (1) to enter an anion resin column, collecting a third effluent for later use, enabling the second effluent obtained in the step (1) to serve as a desorbent to enter the anion resin column, and respectively collecting a first-stage effluent with the pH value of 3.3 to neutral and a second-stage effluent with the pH value of less than 3.3;
(3) performing ultrafiltration and nanofiltration treatment on the first-stage effluent collected in the step (2), wherein the collected trapped fluid is a potassium phytate solution; taking the second-stage effluent collected in the step (2) as a desorbent of the next batch of the cationic resin column, and introducing the second-stage effluent into the cationic resin column, wherein the collected effluent is used as a desorbent component of the next batch of the anionic resin column in the step (2);
(4) filtering the third effluent collected in the step (2) by using an ultrafiltration membrane, fermenting the collected trapped fluid, filtering the collected permeate by using a nanofiltration membrane, and respectively collecting the trapped fluid and the permeate for later use;
(5) spray drying the trapped fluid for later use in the step (4) to obtain a corn protein powder product; treating the reserved permeate with a reverse osmosis membrane, and respectively collecting the trapped fluid and the permeate for later use;
(6) carrying out vacuum concentration and vacuum distillation treatment on the trapped liquid collected in the step (5) to obtain a lactic acid product; and (4) mechanically applying the permeate collected in the step (5) as process production water.
2. The corn steep water treatment method according to claim 1, characterized in that: the resin in the cation resin column in the step (1) is strong acid cation resin, the type of the resin is Hairun HAD-10 resin, and the volume of the resin in the cation resin column is 3 BV.
3. The corn steep water treatment method according to claim 1, characterized in that: the concentration of the hydrochloric acid in the step (1) is 8-10% w/v, the volume of the hydrochloric acid is 1.3-2 times of the volume of the resin in the cation resin column, and the hydrochloric acid enters the cation resin column at the flow rate of 0.5 BV/h.
4. The corn steep water treatment method according to claim 1, characterized in that: and (3) in the step (2), the resin in the anion resin column is a weak base anion exchange resin, and the type of the resin is weak base acrylic resin ZG 312.
5. The corn steep water treatment method according to claim 1, characterized in that: adding fermentation strains when the trapped fluid collected in the step (4) is fermented, stirring for 10-15min every 3h, maintaining the fermentation temperature at 30-50 ℃, and fermenting and stirring for 7-10 days.
6. The corn steep water treatment method according to claim 1, characterized in that: the molecular weight cut-off of the ultrafiltration membrane is 10-20 ten thousand, the molecular weight cut-off of the nanofiltration membrane is 500-600, and the molecular weight cut-off of the reverse osmosis membrane is less than 100.
7. The corn steep water treatment method according to claim 1, characterized in that: standing the corn soaking water in the step (1) for 4-6h at the temperature of 45-50 ℃.
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| CN113735136A (en) * | 2021-09-09 | 2021-12-03 | 诸城市浩天药业有限公司 | Process method for preparing potassium salt and byproduct magnesium salt by using corn soaking water |
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| CN115212985A (en) * | 2022-06-22 | 2022-10-21 | 江苏力德尔电子信息技术有限公司 | Polylactic acid modified plastic preparation facilities |
| CN116462168A (en) * | 2023-03-24 | 2023-07-21 | 诸城市浩天药业有限公司 | Production process of plant source monopotassium phosphate |
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