CN112299651B - Method for treating rice milk water for brewing yellow rice wine - Google Patents
Method for treating rice milk water for brewing yellow rice wine Download PDFInfo
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- CN112299651B CN112299651B CN202011078646.3A CN202011078646A CN112299651B CN 112299651 B CN112299651 B CN 112299651B CN 202011078646 A CN202011078646 A CN 202011078646A CN 112299651 B CN112299651 B CN 112299651B
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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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
- C02F2103/325—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters from processes relating to the production of wine products
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/12—Activated sludge processes
- C02F3/1236—Particular type of activated sludge installations
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Abstract
The invention relates to a method for treating rice milk water brewed by yellow wine, which comprises the following steps: (1) Firstly adding a combined oxidant into rice pulp water brewed by yellow wine, and then adding a modified nickel-based supported catalyst; wherein the combined oxidant comprises a liquid oxidant and a gaseous oxidant; (2) Carrying out wet low-temperature catalytic oxidation reaction on the mixture obtained in the step (1); wherein the reaction temperature is 100-200 ℃, the reaction pressure is 0.1-2 MPa, and the reaction time is 1-5 h; (3) Filtering the reaction product obtained in the step (2) to obtain filtrate and filter residue; the filtrate is discharged after reaching the standard after biochemical treatment. The invention constructs a catalytic oxidation system by the combination of a liquid oxidant and a gas oxidant and the cooperation of the liquid oxidant and a modified nickel-based supported catalyst, and reduces the temperature of catalytic oxidation reaction to 100-200 ℃; the water quality of the rice milk water brewed by the yellow wine is more stable after the wet low-temperature catalytic oxidation treatment.
Description
Technical Field
The invention belongs to the technical field of yellow wine brewing wastewater treatment, and particularly relates to a treatment method of yellow wine brewing rice milk.
Background
Yellow wine is a special national product and traditional food in China and is one of the oldest alcoholic beverages in the world. In the traditional yellow wine brewing process, glutinous rice needs to be soaked for a period of time, and in the wine brewing by a rice spreading method, the rice soaking time is as long as 16-20 days; soaking rice for 2-3 days in wine brewing by a rice showering method; the time for brewing wine and soaking rice by a rice feeding method is relatively short, and is generally 18-24 hours. The rice milk water is a byproduct in the rice soaking procedure in the yellow wine production, and according to statistics, 1t of yellow wine is produced, and 0.5t of wastewater is produced. The rice milk wastewater has the characteristics of high organic matter content (COD value reaches 10000-30000 mg/L), high total acid content and the like, and if the rice milk wastewater is discharged into rivers without being treated, the rice milk wastewater seriously pollutes water bodies, and seriously threatens industrial and agricultural production, resident life, aquaculture industry and the like.
The prior yellow wine rice milk water treatment methods are various, such as a coagulation sedimentation method, an aerobic biological method, an anaerobic-aerobic combined process, comprehensive recycling and the like, wherein the acidification-anaerobic-aerobic combined process is widely applied. The biochemical method mainly has the problems of large occupied area, large sludge production, poor impact load resistance, high operating cost, large one-time investment and the like. The coagulation sedimentation method comprises a coagulation separation method, an adsorption method, a membrane technology and the like, and the data show that the treatment by the methods has difficult sedimentation of macromolecular substances such as protein, polysaccharide and the like in the rice slurry water, and the removal rate of COD value is not high and is about 30 percent. The rice milk is recycled as the feeding water for producing the yellow wine, the yellow wine is brewed by feeding the fermentation liquor, the using amount of the rice milk is generally 30-40 percent of that of the rice, and because the generating amount of the rice milk is always larger than the recycling amount, the method needs to be researched and developed for efficiently and stably brewing the rice milk by using the yellow wine.
Wet oxidation (WAO) is the oxidation of toxic and harmful organic substances into water and CO by using an oxidant (air, oxygen or ozone) under the condition of high temperature (more than 200 ℃) and high pressure 2 And other small molecular organic matters, and the reaction needs to be carried out at high temperature and high pressure, so the requirements on equipment materials are high, and the investment and the energy consumption are large.
Disclosure of Invention
Based on the above disadvantages and shortcomings of the prior art, it is an object of the present invention to at least address one or more of the above problems in the prior art, in other words, to provide a method of treating rice water for yellow wine brewing that meets one or more of the above needs.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for treating rice milk water for brewing yellow rice wine comprises the following steps:
(1) Firstly adding a combined oxidant into rice slurry water brewed by yellow wine, and then adding a modified nickel-based supported catalyst; wherein the combined oxidant comprises a liquid oxidant and a gaseous oxidant;
(2) Carrying out wet low-temperature catalytic oxidation reaction on the mixture obtained in the step (1); wherein the reaction temperature is 100-200 ℃, the reaction pressure is 0.1-2 MPa, and the reaction time is 1-5 h;
(3) Filtering the reaction product obtained in the step (2) to obtain filtrate and filter residue; the filtrate is discharged after reaching the standard after biochemical treatment.
Preferably, the filter residue is recycled to the step (1) to be used as the catalyst.
Preferably, the liquid oxidant comprises hypochlorous acid or hydrogen peroxide.
Preferably, the gaseous oxidant comprises one or more of air, oxygen, ozone.
Preferably, the modified nickel-based supported catalystThe agent is Ni-Ce/Al 2 O 3 Or Ni-Mg/Al 2 O 3 。
Preferably, the molar ratio of the Ni to the Ce or Mg is 1: (0.01-0.1).
Preferably, the adding amount of the modified nickel-based supported catalyst is 0.01-5% of the rice milk water amount for brewing yellow rice wine.
Preferably, the adding amount of the modified nickel-based supported catalyst is 0.5-2% of the rice milk water amount for brewing yellow rice wine.
Preferably, in the step (2), the reaction temperature is 100 to 150 ℃ and the reaction pressure is 0.5 to 1MPa.
Preferably, the biochemical treatment is activated sludge aeration treatment.
The technical principle of the invention is that under the participation of a special catalyst, various types of oxidants are used as initiators to generate hydroxyl radicals under certain temperature and pressure conditions so as to oxidize and decompose organic matters in the rice pulp wastewater from yellow wine brewing. The hydroxyl radical is an oxidant with small selectivity, when various organic pollutants exist in water, the organic pollutants can be almost removed at the same time, partial organic matters can be efficiently and completely oxidized and decomposed into harmless components such as carbon dioxide, water and the like, the COD (chemical oxygen demand) of the wastewater is reduced, so that the biochemical load is reduced, the biochemical residence time is reduced, the floor area of a biochemical system is reduced, the investment is reduced, the water quality after low-temperature catalytic oxidation treatment is more stable, and the operation of the biochemical system is more stable.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention constructs a catalytic oxidation system by the combination of liquid oxidant and gas oxidant and the cooperation of the liquid oxidant and the modified nickel-based supported catalyst, and reduces the temperature of catalytic oxidation reaction to 100-200 ℃; after the rice milk water brewed by the yellow wine is subjected to wet low-temperature catalytic oxidation treatment, the water quality is more stable, and the operation of a biochemical system is more stable.
(2) The wet low-temperature catalytic oxidation technology can efficiently and completely oxidize and decompose partial organic matters into harmless components such as carbon dioxide, water and the like, and reduce the COD of the wastewater, thereby lightening the biochemical load, reducing the biochemical retention time, reducing the occupied area of a biochemical system and reducing the investment.
(3) Wet low-temp catalytic oxidation does not produce sludge and SO x 、NO x Harmful secondary pollution gas is generated, and no secondary hazardous waste is generated.
(4) The wet low-temperature catalytic oxidation process has the advantages of low investment, high automation degree and small occupied area.
Drawings
FIG. 1 is a flowchart of a method of treating rice mash water produced by yellow wine brewing according to example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following specific examples.
Ni-Ce/Al according to the following examples of the invention 2 O 3 Or Ni-Mg/Al 2 O 3 The catalyst is prepared by an isometric impregnation method, which comprises the following steps:
first, gamma-Al 2 O 3 The carrier is soaked in a metal salt aqueous solution (Ce or Mg) prepared in advance according to the molar ratio of Ni to Ce or Mg for 24 hours, then dried for 5 hours at 383K, and then roasted for 5 hours at 823K in the air atmosphere to prepare the modified gamma-Al 2 O 3 The carrier is ready for use;
then adding a certain amount of Ni (NO) 3 ) 2 Adding modified gamma-Al into the aqueous solution under stirring 2 O 3 Adjusting pH to 8-9 with 10% NaOH aqueous solution, soaking for 12 hr, filtering, washing with deionized water to neutrality, drying the obtained filter cake at 383K for 5h, and calcining at 823K for 5h to obtain Ni-Ce/Al 2 O 3 Or Ni-Mg/Al 2 O 3 A catalyst.
Example 1:
in the method for treating rice milk water for brewing yellow rice wine of the embodiment, the treated wastewater is rice milk wastewater of a certain company, and the COD =13300mg/L.
As shown in fig. 1, the method for treating rice milk water from yellow wine brewing according to the present embodiment includes the following steps:
step 1: 0.5% of Ni-Ce/Al is added into the wastewater 2 O 3 (wherein Ni andthe molar ratio of Ce is 1:0.02 The catalyst (the adding proportion takes the mass of the wastewater as a reference), hydrogen peroxide and oxygen combined oxidant, the temperature is 150 ℃, the pressure is 1MPa, the reaction is carried out for 3 hours, the filtration and the separation are carried out, so as to obtain a filtrate I and a filter residue I, and the COD of the filtrate I is 2740mg/L; the filter residue I is used as a catalyst and can be recycled.
And 2, step: the COD of the filtrate I obtained in the step 1 after the aeration treatment of the activated sludge is 235mg/L.
Comparative example 1:
the treated wastewater is rice milk wastewater of a certain company, and the COD is measured to be =13300mg/L.
The method for treating rice milk water brewed by yellow wine comprises the following steps:
step 1: adding 0.5% of CuSO into the wastewater 4 Taking the mass of the wastewater as a reference, taking oxygen as an oxidant, reacting at the pressure of 2MPa and the temperature of 260 ℃ for 3h, and obtaining liquid COD of 2912mg/L;
and 2, step: COD of the liquid obtained in the step 1 after aeration treatment of activated sludge is 263mg/L.
The wastewater treatment effect of the embodiment 1 is equivalent to that of the comparative example 1, which shows that the catalytic oxidation system is constructed by the modified catalyst and the combined oxidant, the reaction temperature is reduced, and the treatment effect equivalent to that of high-temperature wet catalytic oxidation can be obtained.
Example 2:
the treated wastewater is rice pulp wastewater of a certain company, and COD =30000mg/L is determined.
The treatment method of the rice wine brewing rice milk water comprises the following steps:
step 1: adding 0.5% of Ni-Mg/Al in the wastewater 2 O 3 (the molar ratio of Ni to Mg is 1.02) a catalyst (based on the mass of wastewater), hypochlorous acid and ozone combined oxidant, reacting for 2h at 100 ℃ and 1MPa, filtering and separating to obtain a filtrate I and a filter residue I, wherein the COD of the filtrate I is 1896Mg/L; the filter residue I is a catalyst and can be recycled.
Step 2: the COD of the filtrate I obtained in the step 1 after the aeration treatment of the activated sludge is 234mg/L.
Comparative example 2:
the treated wastewater is rice milk wastewater of a certain company, and the COD is determined to be =30000mg/L.
The method for treating rice milk water for brewing yellow wine in the comparative example comprises the following steps:
step 1: 0.5% of Ni-Mg/Al is added into the wastewater 2 O 3 (the molar ratio of Ni to Mg is 1.02) a catalyst (based on the mass of wastewater), reacting for 2 hours at 100 ℃ under 1MPa by using ozone as an oxidant, and filtering and separating to obtain a filtrate I and a filter residue I, wherein the COD of the filtrate I is 8432Mg/L; the filter residue I is a catalyst and can be recycled.
Step 2: and (3) aerating the filtrate I obtained in the step (1) by using activated sludge to obtain COD of 2560mg/L.
Comparative example 3:
the treated wastewater is rice pulp wastewater of a certain company, and COD =30000mg/L is determined.
The method for treating rice milk water for brewing yellow wine in the comparative example comprises the following steps:
step 1, adding 0.5 percent of Ni/Al into the wastewater 2 O 3 The method comprises the following steps of (1) reacting for 2 hours at 100 ℃ and 1MPa by using a catalyst (based on the mass of wastewater) and a hypochlorous acid and ozone combined oxidant to obtain a filtrate I and a filter residue I, wherein COD of the filtrate I is 5923mg/L; the filter residue I is a catalyst and can be recycled.
And 2, aerating the filtrate I obtained in the step 1 by activated sludge to obtain the COD of 1877mg/L.
Example 3:
the treated wastewater is rice pulp wastewater of a certain company, and COD =18500mg/L.
The treatment method of the rice wine brewing rice milk water comprises the following steps:
step 1: adding 5% of Ni-Ce/Al into the wastewater 2 O 3 (the molar ratio of Ni to Ce is 1.01) catalyst (based on the mass of wastewater), hypochlorous acid and air are combined with oxidant, the temperature is 200 ℃, the pressure is 2MPa, the reaction is carried out for 3 hours, and filter residue I is obtained by filtration and separation, wherein the COD of the filter solution I is 6510mg/L; the filter residue I is a catalyst and can be recycled.
Step 2: and (3) aerating the filtrate I obtained in the step (1) by using activated sludge to obtain the COD of 2615mg/L.
Example 4:
the treated wastewater is rice pulp wastewater of a certain company, and COD =18500mg/L.
The treatment method of the rice wine brewing rice milk water comprises the following steps:
step 1: adding 0.01% of Ni-Ce/Al into the wastewater 2 O 3 (the molar ratio of Ni to Ce is 1: 0.1) catalyst (based on the mass of wastewater), hypochlorous acid and air are combined with oxidant, the temperature is 200 ℃, the pressure is 2MPa, the reaction is carried out for 3h, and filtration and separation are carried out to obtain filtrate I and filter residue I, wherein COD of the filtrate I is 9235mg/L; the filter residue I is a catalyst and can be recycled.
And 2, aerating the filtrate I obtained in the step 1 by using activated sludge, wherein the COD of the filtrate I is 4890mg/L.
In the above examples and alternatives, the reaction temperature may be 120 ℃, 135 ℃, 160 ℃, 180 ℃, etc., the reaction pressure may be 0.1MPa, 0.5MPa, 0.8MPa, 1.5MPa, etc., and the reaction time may be 1h, 1.5h, 2.5h, 4h, 5h, etc.
In the above examples and alternatives, the amount of catalyst added relative to the mass of wastewater may also be 0.1%, 0.5%, 1.5%, 2%, 2.5%, 3%, 4.5%, etc.
In the above examples and alternatives, the molar ratio of Ni to Ce may also be 1.
In the above embodiments and alternatives, the gaseous oxidant may also be a plurality of air, oxygen, ozone.
The foregoing has outlined rather broadly the preferred embodiments and principles of the present invention and it will be appreciated that those skilled in the art may devise variations of the present invention that are within the spirit and scope of the appended claims.
Claims (8)
1. The treatment method of rice milk water for brewing yellow rice wine is characterized by comprising the following steps of:
(1) Firstly adding a combined oxidant into rice slurry water brewed by yellow wine, and then adding a modified nickel-based supported catalyst; wherein the combined oxidant comprises a liquid oxidant and a gas oxidant, and the modified nickel-based supported catalyst is Ni-Mg/Al 2 O 3 The molar ratio of Ni to Mg is 1: (0.01-0.1);
(2) Carrying out wet low-temperature catalytic oxidation reaction on the mixture obtained in the step (1); wherein the reaction temperature is 100-200 ℃, the reaction pressure is 0.1-2 MPa, and the reaction time is 1-5 h;
(3) Filtering the reaction product obtained in the step (2) to obtain filtrate and filter residue; the filtrate is discharged after reaching the standard after biochemical treatment.
2. The method for treating rice milk water produced by brewing yellow rice wine according to claim 1, wherein the filter residue is recycled to step (1) to be used as a catalyst.
3. The method for treating rice wine brewing water as claimed in claim 1, wherein the liquid oxidant comprises hypochlorous acid or hydrogen peroxide.
4. The method for treating rice-based serofluid from yellow rice wine brewing as claimed in claim 1, wherein the gaseous oxidant comprises one or more of air, oxygen and ozone.
5. The method for treating rice milk water brewed by yellow rice wine of claim 1, wherein the adding amount of the modified nickel-based supported catalyst is 0.01-5% of the water amount of the rice milk water brewed by yellow rice wine.
6. The method for treating rice milk water brewed by yellow rice wine according to claim 1, wherein the adding amount of the modified nickel-based supported catalyst is 0.5-2% of the rice milk water brewed by yellow rice wine.
7. The method for treating rice milk water for yellow wine brewing according to claim 1, wherein in the step (2), the reaction temperature is 100-150 ℃ and the reaction pressure is 0.5-1 MPa.
8. The method for treating rice milk water produced by brewing yellow rice wine according to claim 1, wherein the biochemical treatment is activated sludge aeration treatment.
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| CN101844828B (en) * | 2010-05-27 | 2011-12-14 | 南京工业大学 | Treatment method for efficient catalytic oxidation of chlor-alkali industrial wastewater |
| CN103193365A (en) * | 2013-04-25 | 2013-07-10 | 湖北理工学院 | Method and device for treating high-concentrated organic wastewater through combination of ozone oxidation and biological filtration oxidation |
| CN106492785A (en) * | 2016-08-31 | 2017-03-15 | 浙江奇彩环境科技股份有限公司 | A kind of catalyst and its method of wastewater treatment for dye wastewater treatment |
| CN106693974A (en) * | 2016-11-11 | 2017-05-24 | 大连理工大学 | Preparation method and application of supported metal oxide catalyst for removing ammonia nitrogen in water through catalytic ozonation |
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