CN113233507B - Method for preparing basic chromium sulfate from residual liquid in menadione production - Google Patents
Method for preparing basic chromium sulfate from residual liquid in menadione production Download PDFInfo
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Abstract
The invention provides a method for preparing basic chromium sulfate from residual liquid in menadione production, which comprises the following steps: (1) aging and solid-liquid separating the residual liquid for producing menadione in sequence to obtain treated liquid; (2) mixing the treated liquid obtained in the step (1) with a hexavalent chromium source, sequentially carrying out primary reduction and secondary reduction on the obtained mixed material, and concentrating to obtain a reduced feed liquid; (3) the reduced feed liquid is subjected to curing, fine filtration and spray drying in sequence to obtain basic chromium sulfate; the method of the invention adds the steps of aging and solid-liquid separation before reduction, and selects a fine filtration mode during reduction, thereby obviously improving the product quality of the basic chromium sulfate.
Description
Technical Field
The invention relates to the technical field of waste liquid treatment, in particular to a method for preparing basic chromium sulfate from residual liquid in menadione production.
Background
The traditional basic chromium sulfate is produced by dissolving sodium bichromate in water, adding a certain amount of sulfuric acid, mixing, reducing with glucose to obtain a solution, and spray-drying the solution to obtain the basic chromium sulfate. Because the chromium resource is precious, the full utilization of the precious chromium resource and the reduction and elimination of the pollution of chromium to the environment are the development routes of chromium salt enterprises.
2-methyl-1, 4 naphthoquinone is an intermediate for preparing feed additive vitamin k3, and is prepared by oxidizing raw material 2-methylnaphthalene with sodium bichromate strongly acidic solution as oxidant, and filtering to separate out 2-methyl-1, 4 naphthoquinone intermediate for synthesizing vitamin k3 product. Meanwhile, a large amount of generated naphthoquinone residual liquid contains a large amount of hexavalent chromium and strong acid, and if the naphthoquinone residual liquid is not utilized, not only can resources be greatly wasted, but also serious environmental pollution can be caused. However, the menadione residual liquid contains methylnaphthalene and derivatives thereof, and if the methylnaphthalene and the derivatives thereof cannot be effectively removed, the quality of the basic chromium sulfate can be seriously influenced.
In order to fully utilize the residual liquid obtained by menadione production, CN107720824A discloses a process for preparing chrome green by a sulfur method from k3 residual liquid, which comprisesTwo sections, one section: neutral leaching yellow water or sodium chromate alkaline solution is adopted as a raw material in a workshop, liquid alkali is added according to a proportion to adjust the alkalinity, the mixture is heated to a certain temperature on an electric furnace, ground sulfur paste is added, and after the pre-reaction is finished, the mixture is cured for a period of time; after filtering, washing with water to ensure that Na is contained in the last washing water 2 S 2 O 3 And (4) content. Calcining the dried filter cake in a muffle furnace to obtain a crude chromium green product, and washing and drying the crude chromium green product to obtain metallurgical-grade chromium green; and a second stage: mixing the filtrate after the chromium hydroxide completely reacts with washing water, adding sodium chromate alkali solution, heating and stirring, adding k3 residual liquid at a certain temperature to adjust pH, aging for a certain time, filtering to measure Na in the filtrate 2 S 2 O 3 Filtering, washing and roasting the filter cake, and washing, drying and grinding the chrome green semi-finished product to obtain the pigment-grade chrome green.
CN111943267A discloses a method for preparing chromium trioxide from vitamin k3 raffinate, which comprises the following steps: mixing the residual vitamin k3 liquid with a hexavalent chromium salt solution and a reducing agent, and reacting to obtain a reducing solution; mixing the obtained reduction solution with a hexavalent chromium salt solution, heating, and adjusting the pH value to generate chromium chromate precipitate; and calcining the chromium chromate precipitate to obtain chromium sesquioxide.
However, the preparation of chromium sesquioxide by using the vitamin k3 residual liquid has the problems of large equipment capital investment, large site requirement amount and the like, and a new recovery idea of the vitamin k3 residual liquid needs to be created.
CN104386752A discloses a method for preparing basic chromium sulfate by using residual liquid obtained from menadione production, which comprises the following steps: and uniformly mixing the concentrated residual liquid and industrial sugar according to a certain molar ratio, and reacting for 0.5-4 h in a pressure reaction kettle at 100-300 ℃ and 0-4 MPa. After the reaction is finished, reducing a small amount of hexavalent chromium which is not reacted in the feed liquid into trivalent chromium by using a reducing agent, adjusting the basicity of the feed liquid by using an alkaline solution, filtering, and spray-drying the filtrate to prepare the basic chromium sulfate product. However, the step is carried out under the pressurization condition, the operation condition is harsh, and the defects that the organic matter content in the basic chromium sulfate is high, and because the reduction reaction is complicated, and some incompletely oxidized intermediate products such as oxalic acid, formic acid, acetic acid, aldehydes and a small amount of sugar are hard to remove by carbonization and other impurities, the tanned blue leather is stained and dark in color, not bright and bright in color and the like during terminal use are caused.
Therefore, there is a need to develop an improved method for preparing basic chromium sulfate by using the residual liquid obtained from menadione production, which can improve the operation simplicity and reduce the content of water-insoluble substances such as menadione and organic impurities generated by reduction side reaction in the basic chromium sulfate.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing basic chromium sulfate from residual liquid for producing menadione, which adds the steps of aging and solid-liquid separation before reduction, and selects a fine filtration mode after reduction, so that chromium in the k3 residual liquid can be completely recovered, the operation is simple and convenient, the problem of poor product quality in the conventional production of basic chromium sulfate from the residual liquid for producing menadione is solved, and the prepared basic chromium sulfate product can be widely used for leather tanning, mordanting, dyes, ceramic glaze colors, trivalent chromium electroplating or preparation of chromium salt products and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing basic chromium sulfate from residual liquid in menadione production, which comprises the following steps:
(1) aging and solid-liquid separating the residual liquid for producing menadione to obtain treated liquid;
(2) mixing the treated liquid obtained in the step (1) with a hexavalent chromium source, sequentially carrying out first reduction and second reduction on the obtained mixed material, and concentrating to obtain reduced feed liquid;
(3) and sequentially curing, fine filtering and spray drying the reduced feed liquid to obtain the basic chromium sulfate.
According to the method for preparing the basic chromium sulfate from the residual liquid for producing the menadione, provided by the invention, the vitamin k3 residual liquid, namely the residual liquid for producing the menadione is aged firstly and then subjected to solid-liquid separation, so that the further separation of the menadione from the residual liquid is realized, and the content of the menadione in subsequent products is effectively reduced. And then adding a hexavalent chromium source for mixing, so that excessive acid can be consumed, and a solution environment is provided for reducing and generating basic chromium sulfate. The invention also sets the fine filtration step after the aging, removes the residual impurities in the liquid, and is assisted with the early-stage aging and solid-liquid separation, wherein the fine filtration step can reduce the content of residual water-insoluble substances in the liquid, such as menadione or organic impurities generated by reduction side reaction thereof, reduce the impurities such as carbonized solid phase and the like generated in the reduction process, and remarkably improve the product quality of the basic chromium sulfate.
The technical principle is as follows: the inventor finds that menadione in the residual liquid for producing menadione is easy to be entrained in the product in the process of preparing basic chromium sulfate, the quality of the product is reduced, and although the basic chromium sulfate with qualified chromium trioxide content and alkalinity can be obtained, the residual of menadione and other impurities greatly influences the use of the subsequent basic chromium sulfate. Through exploration and research, the inventor finds that menadione is gradually aggregated and solidified with other impurities in the residual liquid in the aging process, and the content of menadione and other impurities in the residual liquid can be reduced through solid-liquid separation subsequently, so that the purity of the product is finally improved; the early-stage aging is matched with the fine filtration after reduction, and the basic chromium sulfate product with excellent product quality can be prepared.
Preferably, the concentration of hexavalent chromium in the menadione production raffinate is 62-66 g/L, for example, 62g/L, 63g/L, 64g/L, 65g/L or 66g/L, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the concentration of sulfuric acid in the menadione production raffinate is 100-135 g/L, such as 100g/L, 104g/L, 108g/L, 112g/L, 116g/L, 120g/L, 124g/L, 128g/L, 132g/L or 135g/L, but not limited to the recited values, and other unrecited values in the range are also applicable.
Preferably, the menadione-producing raffinate contains naphthalene-containing organic substances.
Preferably, the naphthalene containing organic substance comprises any one of menadione, methylnaphthalene or methylnaphthalene derivative or a combination of at least two thereof, wherein typical but non-limiting combinations are menadione and methylnaphthalene, and methylnaphthalene derivative.
Preferably, the concentration of the naphthalene-containing organic substance in the menadione production residual liquid is 0.0001-0.0005 g/L, such as 0.0001g/L, 0.0002g/L, 0.00023g/L, 0.00028g/L, 0.0003g/L, 0.00035g/L, 0.0004g/L or 0.0005g/L, but not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the aging time in step (1) is 48 to 120 hours, such as 48 hours, 56 hours, 64 hours, 72 hours, 80 hours, 88 hours, 96 hours, 104 hours, 112 hours or 120 hours, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the aging temperature is normal temperature.
The normal temperature refers to a temperature environment without heating or cooling, generally about 25 ℃, and can be adjusted according to environmental changes.
Preferably, the solid-liquid separation comprises filtration, preferably plate and frame filtration.
Preferably, the hexavalent chromium source in step (2) comprises sodium red vanadium, preferably a 60-degree sodium red vanadium mother liquor.
The adding amount of the hexavalent chromium source is not particularly limited, and the hexavalent chromium source is reduced to the amount of the hexavalent chromium source required by calculating basic chromium sulfate with the alkalinity of 31-35%, preferably 33.3%.
Preferably, the method further comprises a step of solid-liquid separation of the mixed materials before the first reduction.
Preferably, the solid-liquid separation mode of the mixed materials comprises filtration, preferably plate-and-frame filtration.
Preferably, the reducing agent of the first reduction in step (2) comprises glucose.
Preferably, the second reducing agent comprises sodium metabisulfite.
Preferably, the sodium metabisulfite is added in an amount of 0.0005 to 0.001kg/L, for example, 0.0005kg/L, 0.0006kg/L, 0.0007kg/L, 0.0008kg/L, 0.0009kg/L, 0.001kg/L or 0.001kg/L, and the like, but not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the temperature of the first reduction in step (2) is 100 to 105 ℃, for example, 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃ or 105 ℃, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.
According to the invention, the first reduction is preferably carried out under a micro-boiling condition, namely at 100-105 ℃, and similar to the prior art, an indicator is adopted for detection in the reduction process, and a detection method commonly used in the field can be adopted for detection. This can be carried out, for example, by the following method:
when the mixed materials are changed from olive color to dark green color, the indicator is used for checking, if the indicator is red, the reducing agent is continuously added, and when the indicator is changed into dark purple, the reducing agent for the first reduction can be stopped from being added, and slight boiling is kept until the indicator is detected to be developed without red, and then the mixture enters the second reduction.
Preferably, the indicator comprises diphenylcarbodihydrazide.
Preferably, the pressure of the first reduction is atmospheric pressure.
The first reduction is not required to be pressurized or decompressed, the first reduction can be carried out under the normal pressure condition, the operation is simple and convenient, a pressure container is not required, and the production cost is low.
Preferably, the temperature of the second reduction is 100 to 105 ℃, for example, 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃ or 105 ℃, but not limited to the recited values, and other values not recited in the range are also applicable.
The second reduction is preferably carried out under the condition of slight boiling, the concentration and the second reduction can be simultaneously carried out, and the conversion of hexavalent chromium to trivalent chromium in the system can be more thoroughly realized.
Preferably, the pressure of the second reduction is atmospheric pressure.
The second reduction is not required to be pressurized or decompressed, the second reduction can be carried out under the normal pressure condition, the operation is simple and convenient, a pressure container is not required, and the production cost is low. Preferably, the first reduction and the second reduction both adopt non-pressure vessel enamel reaction kettles.
Preferably, the concentration of the reduced feed liquid in the step (2) is 48 to 52 baume degrees, for example, 48, 49, 50, 51 or 52, but is not limited to the values listed, and other values not listed in the range are also applicable.
Preferably, the temperature of the aging in the step (3) is 50 to 70 ℃, for example, 50 ℃, 52 ℃, 55 ℃, 60 ℃, 62 ℃, 65 ℃, 68 ℃ or 70 ℃, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the aging time is 48 to 72 hours, for example, 48 hours, 49 hours, 52 hours, 54 hours, 56 hours, 58 hours, 60 hours, 62 hours, 66 hours, 68 hours or 72 hours, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the fine filtering in step (3) comprises: and filtering the cured feed liquid by using a precision filter.
The reducing agent may generate phenomena such as carbonization and the like in the reduction process, so that the content of impurities in the product is high, and the purity of the product can be improved through the fine filtration process.
Preferably, the fine filter has an average pore size in the range of 1 to 5 μm, for example, 1 μm, 1.2 μm, 1.5 μm, 1.8 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm or 5 μm, but is not limited to the values listed, and other values not listed in this range are also applicable.
Preferably, the inlet temperature of the spray drying is 170 to 200 ℃, for example, 170 ℃, 175 ℃, 180 ℃, 190 ℃, 195 ℃, 196 ℃, 197 ℃, 198 ℃, or 200 ℃, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the exit temperature of the spray drying is 84 to 90 ℃, for example 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃ or 90 ℃ and the like, but is not limited to the recited values, and other values not recited in the range are also applicable.
The spray drying according to the invention is further preferably carried out using a drying tower. The invention further controls the temperature of hot air at an inlet and an outlet, fine-filtered feed liquid is conveyed to the tower through a pump to rotate an atomizing disc for atomization, the hot air is evaporated and dried instantly, the feed and the discharge are carried out simultaneously, the drying time is automatically matched according to the concentration of the feed liquid, the flow process is carried out, and the drying time is not specially limited.
Preferably, the content of chromium trioxide in the basic chromium sulfate in the step (3) is 24 to 26%, for example, 24%, 24.3%, 24.5%, 24.7%, 24.9%, 25.2%, 25.4%, 25.6%, 25.8%, or 26%, etc., but not limited to the above-mentioned values, and other values not listed in this range are also applicable.
Preferably, the basicity of the basic chromium sulfate is 31 to 35%, and may be, for example, 31%, 31.5%, 31.9%, 32.4%, 32.8%, 33.3%, 33.7%, 34.2%, 34.6%, 35%, or the like, but is not limited to the values listed, and other values not listed in this range are also applicable.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) aging the residual liquid for producing menadione for 48-120 h and filtering by a plate frame to obtain a treated liquid;
(2) mixing the treated liquid obtained in the step (1) with a 60-degree sodium vanadic acid mother liquor, filtering the obtained mixed material by using a plate frame, performing 100-105 ℃ micro-boiling first reduction on the filtered mixed material by using glucose, adding 0.0005-0.001 kg/L of sodium metabisulfite, performing 100-105 ℃ micro-boiling second reduction on the filtered mixed material, and concentrating the obtained product to obtain reduced feed liquid with the concentration of 48-52 baume degrees;
(3) and curing the reduced feed liquid at 50-70 ℃ for 48-72 h, and performing fine filtration and spray drying by using a fine filtration filter with the aperture range of 1-5 mu m to obtain basic chromium sulfate with the chromium trioxide content of 24-26% and the alkalinity of 31-35%.
In the present invention, "%" of each component content means "% by weight" unless otherwise specified.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the method for preparing the basic chromium sulfate from the residual liquid in the menadione production can fully recover the chromium element, and achieves the aims of zero pollution discharge and environmental protection;
(2) according to the method for preparing the basic chromium sulfate from the residual liquid for producing menadione, provided by the invention, the vitamin k3 residual liquid is utilized to research and develop the basic chromium sulfate, the utilization rate of raw materials is improved, the content of chromium sesquioxide can be controlled to be between 24 and 26 percent, preferably between 25.4 and 25.6 percent, the alkalinity is controlled to be between 31 and 35 percent, preferably between 33.3 and 33.6 percent, and the research and development of new varieties meet the market demand;
(3) according to the method for preparing the basic chromium sulfate from the residual liquid for producing the menadione, provided by the invention, through the steps of aging and fine filtering, the content of the menadione after aging and filtering the k3 residual liquid after aging is less than or equal to 0.0001g/L and even can be lower than the detection limit, the product quality of the basic chromium sulfate is obviously improved, wherein the content of water-insoluble substances is less than or equal to 0.03 percent, and the content of iron is less than or equal to 0.004 percent, the tannage blue skin prepared by using the prepared basic chromium sulfate at a terminal is bright in color and free from the problem of dark pollution, and the problem of dark pollution when the basic chromium sulfate prepared from the k3 residual liquid is used for preparing the tannage blue skin is solved.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This example provides a process for preparing basic chromium sulfate from menadione production raffinate, comprising the steps of:
(1) residual liquid for producing menadione (the concentration of hexavalent chromium is 64g/L, the hexavalent chromium exists in the form of sodium bichromate, the concentration of sulfuric acid is 120g/L, and the menadione is 0.00028 g/L) is aged for 72 hours at the normal temperature of 25 ℃ and filtered by a plate frame to obtain treated liquid;
(2) mixing the treated liquid obtained in the step (1) with a 60-DEG red sodium vanadium mother liquid, filtering the obtained mixed material by a plate frame, then carrying out microboiling first reduction at 101 ℃ by glucose, checking by using an indicator when the mixed material is changed from yellow to dark green, continuing adding the reducing agent if the indicator is red, stopping adding the reducing agent for the first reduction when the color of the indicator is changed to dark purple, and keeping microboiling until the indicator is detected to be developed without red, and entering second reduction; the indicator is diphenyl carbonyl dihydrazide;
adding 0.0008kg/L sodium metabisulfite, carrying out second reduction by micro-boiling at 103 ℃, and concentrating to obtain reduced feed liquid with the concentration of 50 +/-2 Baume degrees;
(3) and sequentially curing the reduced feed liquid at 56 ℃ for 48h, fine-filtering the feed liquid by a precision filter with the pore diameter of 1 mu m and spray-drying the feed liquid at an inlet temperature of 197 ℃ and an outlet temperature of 89 ℃ to obtain the basic chromium sulfate.
Example 2
This example provides a process for preparing basic chromium sulfate from menadione production raffinate comprising the steps of:
(1) residual liquid for producing menadione (the concentration of hexavalent chromium is 66g/L, hexavalent chromium exists in the form of sodium bichromate, the concentration of sulfuric acid is 135g/L, menadione is 0.0003 g/L) is aged for 48 hours at the normal temperature of 25 ℃ and filtered by a plate frame to obtain treated liquid;
(2) mixing the treated liquid obtained in the step (1) with a 60-DEG red sodium vanadium mother liquid, filtering the obtained mixed material by a plate frame, then carrying out micro-boiling first reduction at 105 ℃ by glucose, checking by using an indicator when the mixed material is changed from yellow to dark green, continuing adding the reducing agent if the indicator is red, stopping adding the reducing agent for the first reduction when the color of the indicator is changed to dark purple, and keeping micro-boiling until the indicator is detected to be developed without red, and entering second reduction; the indicator is diphenyl carbonyl dihydrazide;
adding 0.0005kg/L sodium metabisulfite, carrying out micro-boiling second reduction at 105 ℃, and concentrating to obtain reduced feed liquid with the concentration of 50 +/-2 Baume degrees;
(3) and curing the reduced feed liquid at 60 ℃ for 40 hours, fine-filtering the feed liquid by a precision filter with the aperture of 1 mu m, and spray-drying the feed liquid at the inlet temperature of 198 ℃ and the outlet temperature of 87 ℃ to obtain the basic chromium sulfate.
Example 3
This example provides a process for preparing basic chromium sulfate from menadione production raffinate comprising the steps of:
(1) residual liquid for producing menadione (the concentration of hexavalent chromium is 62g/L, hexavalent chromium exists in the form of sodium bichromate, the concentration of sulfuric acid is 100g/L, menadione is 0.00025 g/L) is aged for 120h at the normal temperature of 25.5 ℃ and filtered by a plate frame to obtain treated liquid;
(2) mixing the treated liquid obtained in the step (1) with 60-degree sodium vanadic acid mother liquor, filtering the obtained mixed material by a plate frame, performing micro-boiling first reduction at 100 ℃ by glucose, checking by using an indicator when the mixed material is changed from yellow to dark green, continuing adding the reducing agent if the indicator is red, stopping adding the reducing agent for the first reduction when the color of the indicator is changed to dark purple, and keeping micro-boiling until the indicator detects that the color is red and the indicator is not red, and performing second reduction; the indicator is diphenyl carbonyl dihydrazide;
adding 0.001kg/L sodium metabisulfite, carrying out a second reduction by slight boiling at 100 ℃, and concentrating to obtain reduced feed liquid with the concentration of 50 +/-2 Baume degrees;
(3) and (3) aging the reduced feed liquid at 70 ℃ for 60h, fine filtering the feed liquid by a precision filter with the pore diameter of 5 mu m, and spray drying the feed liquid at an inlet temperature of 196 ℃ and an outlet temperature of 90 ℃ to obtain the basic chromium sulfate.
Example 4
This example provides a process for preparing basic chromium sulfate from menadione production raffinate which is the same as in example 1 except that the aging time is only 5 hours.
The basic chromium sulfate prepared in the embodiments 1-4 is used for preparing tanned blue leather at a terminal, the color is bright, the problem of dark pollution is avoided, and the problem of dark pollution when the basic chromium sulfate prepared from the existing k3 residual liquid is used for preparing tanned blue leather is solved.
Comparative example 1
This comparative example provides a process for preparing basic chromium sulfate from menadione-producing raffinate, which was conducted using menadione-producing raffinate of example 1 and the process of example 1 of CN 104386752A.
Comparative example 2
This comparative example provides a process for preparing basic chromium sulfate from menadione production raffinate, which is the same as example 1 except that no aging step is performed.
Comparative example 3
This comparative example provides a process for preparing basic chromium sulfate from menadione residue, which is the same as example 1 except that the fine filtration step is performed instead of the plate-and-frame filtration.
When the basic chromium sulfate prepared in the comparative examples 1-3 is used for preparing the tanned blue leather at a terminal, the color of the tanned blue leather is dark, and the quality of the prepared tanned blue leather is poor.
The test method comprises the following steps: the method comprises the steps of detecting the content of chromium sesquioxide in basic chromium sulfate by using a GB/T24331-2009 method, detecting the alkalinity in the basic chromium sulfate by using a GB/T24331-2009 method, detecting the content of iron in the basic chromium sulfate by using a GB/T24331-2009 method, detecting the menadione content before and after aging and filtering k3 residual liquid by using a spectrophotometer method, and detecting the content of water-insoluble substances in the basic chromium sulfate by using a GB/T24331-2009 method.
The test results of the above examples and comparative examples are shown in table 1.
TABLE 1
From table 1, the following points can be seen:
(1) it can be seen from the comprehensive examples 1 to 3 that the method for preparing basic chromium sulfate from the residual liquid for producing menadione provided by the invention can control the reaction temperature to be less than or equal to 105 ℃, is safe and simple to operate, separates menadione, partially crystallized sodium sulfate and water-insoluble substances from the residual liquid through an aging step, obviously improves the content of chromium sesquioxide in the product, reduces the menadione content in the k3 residual liquid to be less than 0.0001g/L and even lower than a detection limit, ensures that the content of the water-insoluble substances in the final basic chromium sulfate product is less than or equal to 0.03%, and ensures that the alkalinity and the content of the chromium sesquioxide both meet market requirements; and also;
(2) as can be seen from the comprehensive example 1 and the comparative examples 2-3, the content of water insoluble substances in the product is reduced by more than 50% by combining aging, filtering and fine filtering of k3 residual liquid, and the blue leather applied to tanning is obviously improved in color and bright;
(3) by combining example 1 and example 4, it can be seen that the aging time in example 1 is 72h, compared with the aging time in example 4 of 5h, the content of water-insoluble substances in example 1 is only 0.01%, the menadione content after aging and filtering is lower than the detection limit, while the content of water-insoluble substances in example 4 is 0.02%, and the menadione content after aging and filtering is 0.0001g/L, thereby showing that the aging time is further optimized, and the product quality of the basic chromium sulfate can be further improved.
In conclusion, the method for preparing the basic chromium sulfate from the residual liquid for producing the menadione, which is provided by the invention, adds the steps of aging and solid-liquid separation before reduction, and selects a fine filtration mode for reduction, so that the product quality of the basic chromium sulfate is obviously improved, the menadione content in the residual liquid of k3 can be reduced to be below 0.0001g/L and even lower than the detection limit, the water insoluble content of the final basic chromium sulfate product is less than or equal to 0.03%, and the alkalinity and the chromium sesquioxide content both meet the market requirements.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must rely on the above detailed process equipment and process flow to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (18)
1. A method for preparing basic chromium sulfate from menadione production raffinate, which is characterized by comprising the following steps:
(1) aging and solid-liquid separating the residual liquid for producing menadione to obtain treated liquid; the aging time is 48-120 h; the menadione content is less than 0.0001g/L after aging and filtering;
(2) mixing the treated liquid obtained in the step (1) with a hexavalent chromium source, sequentially carrying out first reduction and second reduction on the obtained mixed material, and concentrating to obtain reduced feed liquid; the second reducing reductant comprises sodium metabisulfite; the temperature of the first reduction and the temperature of the second reduction are both 100-105 ℃;
(3) the reduced feed liquid is subjected to curing, fine filtration and spray drying in sequence to obtain basic chromium sulfate;
the content of the water insoluble matter of the basic chromium sulfate is less than or equal to 0.03 percent.
2. The method of claim 1, wherein the solid-liquid separation comprises filtration.
3. The method of claim 2, wherein the solid-liquid separation is plate and frame filtration.
4. The process of claim 1 wherein the source of hexavalent chromium in step (2) comprises sodium vanadium oxide.
5. The process of claim 4 wherein the source of hexavalent chromium in step (2) is 60 degrees sodium vanadyl mother liquor.
6. The method of claim 1, further comprising a step of solid-liquid separating the mixed material before the first reduction.
7. The method of claim 6, wherein the solid-liquid separation of the mixed materials comprises filtration.
8. The method according to claim 7, wherein the solid-liquid separation mode of the mixed materials is plate-and-frame filtration.
9. The method of claim 1, wherein the first reduced reducing agent in step (2) comprises glucose.
10. The method according to claim 1, wherein the sodium metabisulfite is added in an amount of 0.0005 to 0.001 kg/L.
11. The method according to claim 1, wherein the concentration of the reduced feed liquid in the step (2) is 48-52 Baume degrees.
12. The method according to claim 1, wherein the curing temperature in the step (3) is 50 to 70 ℃.
13. The method according to claim 1, wherein the curing time is 48-72 hours.
14. The method of claim 1, wherein the fine filtering in step (3) comprises: and filtering the cured feed liquid by using a precision filter.
15. The method of claim 14, wherein the pore size of the precision filter is in the range of 1 to 5 μm.
16. The method according to claim 1, wherein the basic chromium sulfate in the step (3) has a chromium trioxide content of 24-26%.
17. The method according to claim 1, wherein the basicity of the basic chromium sulfate is 31-35%.
18. Method according to claim 1, characterized in that it comprises the following steps:
(1) aging the residual liquid for producing menadione for 48-120 h and filtering by a plate frame to obtain a treated liquid; aging and filtering to obtain menadione content less than 0.0001 g/L;
(2) mixing the treated liquid obtained in the step (1) with a 60-degree sodium vanadic acid mother liquor, filtering the obtained mixed material by using a plate frame, performing 100-105 ℃ micro-boiling first reduction on the filtered mixed material by using glucose, adding 0.0005-0.001 kg/L of sodium metabisulfite, performing 100-105 ℃ micro-boiling second reduction on the filtered mixed material, and concentrating the obtained product to obtain reduced feed liquid with the concentration of 48-52 baume degrees;
(3) and curing the reduced feed liquid at 50-70 ℃ for 48-72 h, and performing fine filtration and spray drying by using a fine filtration filter with the pore diameter of 1-5 mu m to obtain basic chromium sulfate with the chromium trioxide content of 24-26%, the alkalinity of 31-35% and the water insoluble content of less than or equal to 0.03%.
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