CN113213548A - Packaging method of ferrous chloride crystal - Google Patents

Packaging method of ferrous chloride crystal Download PDF

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Publication number
CN113213548A
CN113213548A CN202110522657.4A CN202110522657A CN113213548A CN 113213548 A CN113213548 A CN 113213548A CN 202110522657 A CN202110522657 A CN 202110522657A CN 113213548 A CN113213548 A CN 113213548A
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Prior art keywords
ferrous chloride
crystals
chloride crystals
packaging
filling
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CN113213548B (en
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车莹
石肖
周小江
龙国兵
梁茂杰
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Tangshan Siruier Chemical Co ltd
Sriel Environmental Science And Technology Co ltd
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Tangshan Siruier Chemical Co ltd
Sriel Environmental Science And Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/10—Halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B31/00—Packaging articles or materials under special atmospheric or gaseous conditions; Adding propellants to aerosol containers
    • B65B31/04—Evacuating, pressurising or gasifying filled containers or wrappers by means of nozzles through which air or other gas, e.g. an inert gas, is withdrawn or supplied
    • B65B31/06—Evacuating, pressurising or gasifying filled containers or wrappers by means of nozzles through which air or other gas, e.g. an inert gas, is withdrawn or supplied the nozzle being arranged for insertion into, and withdrawal from, the mouth of a filled container and operating in conjunction with means for sealing the container mouth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B51/00—Devices for, or methods of, sealing or securing package folds or closures; Devices for gathering or twisting wrappers, or necks of bags
    • B65B51/10—Applying or generating heat or pressure or combinations thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B51/00—Devices for, or methods of, sealing or securing package folds or closures; Devices for gathering or twisting wrappers, or necks of bags
    • B65B51/10—Applying or generating heat or pressure or combinations thereof
    • B65B2051/105—Heat seal temperature control
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Packages (AREA)
  • Gas Separation By Absorption (AREA)
  • Vacuum Packaging (AREA)

Abstract

The invention discloses a packaging method of ferrous chloride crystals, which comprises the following steps: s1, adding reduced iron powder into a ferrous chloride hot concentrated solution with Fe being more than 15%, and adding a small amount of Fe in the ferrous chloride solution3+Reduction; s2, carrying out filter pressing while the solution is hot, cooling the filtrate, crystallizing to separate out ferrous chloride crystals, and carrying out centrifugal separation to obtain ferrous chloride crystals; s3, using a lump crusher to crush the bonded crystals into single crystal grains with uniform particles; s4, using a hot-melt plastic packaging bag, placing a gas distributor connected with nitrogen at the bottom of the plastic bag, filling ferrous chloride crystals to the required weight while filling the nitrogen, and taking the gas distribution disc out of the packaging bag; s5, performing vacuum pumping, nitrogen filling and sealing operation on the filled ferrous chloride by using an external vacuum pumping machine. The invention is packed by breaking the lump, gas distributor and fillingThe technical means of filling nitrogen gas is used for assisting in vacuumizing to remove air existing among the crystals so as to prolong the storage time of the packed ferrous chloride crystals.

Description

Packaging method of ferrous chloride crystal
Technical Field
The invention relates to a compound packaging technology, in particular to a method for preserving and packaging ferrous chloride crystals.
Background
The ferrous chloride crystal is exposed in the air in a large area, is very easy to be oxidized after contacting with oxygen in the air, and cannot easily meet the special requirement of the ferrous chloride crystal in the electronic industry. These industries require Fe in ferrous chloride crystals3+Less than 0.1 percent, is difficult to reach the standard in industrial actual production, and because the ferrous chloride liquid needs to be evaporated and concentrated at high temperature in the production process, ferrous iron is easy to be oxidized in the process, crystals separated out by crystallization cannot be avoided carrying a small amount of Fe3+When Fe is in the ferrous chloride crystal3+Often more than 0.1 percent, and in addition, the product is also easily and rapidly oxidized in the packaging process, and is still easily oxidized by gaps among crystals and air in the package after being packaged, and in addition, the product is transported for a long time, green ferrous chloride crystals are already yellow and Fe is generated when the product arrives at a client3+Indexes can not meet the requirements of customers, and oxidation exists all the time in the production process, the packaging process and the transportation process of the ferrous chloride, so that a method for storing ferrous chloride crystals needs to be developed to prolong the quality guarantee period of products and meet the requirements of actual industrialization.
The preservation method of the ferrous chloride crystal is not disclosed in the patent, and the common vacuum pumping and nitrogen filling preservation technology still has the problem in the preservation of the ferrous chloride crystal. For example, in the direct vacuum-pumping packaging mode, the product is yellowed within one month, and ferrous chloride crystals are seriously bonded, a large or even whole solid structure is formed when the product is unsealed and used, so that the operations such as pouring, weighing, dissolving and the like are inconvenient, and in the vacuum-pumping nitrogen-filling packaging mode, the product still can be yellowed and bonded within two months.
Disclosure of Invention
The invention aims to provide a packaging method of ferrous chloride crystals, which can prevent the ferrous chloride crystals from being oxidized by air in the packaging and transportation processes and prolong the storage time of the ferrous chloride crystals.
In order to solve the technical problems, the adopted technical scheme is as follows:
a packaging method of ferrous chloride crystals comprises the following steps:
s1, adding reduced iron powder into a ferrous chloride hot concentrated solution with Fe being more than 15%, and adding a small amount of Fe in the ferrous chloride solution3+Reduction;
s2, carrying out filter pressing while the solution is hot, cooling the filtrate, crystallizing to separate out ferrous chloride crystals, and separating the ferrous chloride crystals from the liquid by using a centrifugal machine to obtain ferrous chloride crystals;
s3, using a lump crusher to crush the bonded crystals into single crystal grains with uniform particles;
s4, using a hot-melt plastic packaging bag, placing a gas distributor connected with nitrogen at the bottom of the plastic bag, filling ferrous chloride crystals to the required weight while filling the nitrogen, and taking the gas distributor out of the packaging bag;
s5, performing vacuum pumping, nitrogen filling and sealing operation on the filled ferrous chloride by using an external vacuum pumping machine.
Further, the higher the concentration of ferrous chloride is, the higher the crystal precipitation temperature is, the less the amount of reduced iron powder needs to be added, the faster the reaction is, the temperature is controlled to be 60-90 ℃, and the mass ratio of the added reduced iron powder to the solution is as follows: 0.5-1: 1000. The process can effectively reduce Fe in ferrous chloride solution3+The purpose of purifying the ferrous chloride is achieved.
Furthermore, in the operation process, the concentration of the ferrous chloride solution is high, so that the filter pressing work needs to be completed quickly, the ferrous chloride crystals separated out by natural cooling and excessive reduced iron powder are prevented from being separated out of a solution system, the ferrous chloride concentrated solution after filter pressing is cooled and crystallized, and the relatively pure ferrous chloride crystals can be obtained through centrifugal operation.
Furthermore, the lump crusher mainly plays a role in scattering the lump crystals which are bonded in the crystallization and centrifugation processes, eliminating the liquid and air wrapped in the lump crystals, and facilitating the subsequent vacuumizing process to remove the air, water vapor and the like as much as possible.
Furthermore, the gas distributor is placed at the bottom of the plastic bag, nitrogen is filled firstly, the air in the plastic bag is replaced by the nitrogen, ferrous chloride crystals are filled while the nitrogen is filled, the gas distributor is continuously lifted up according to the filling condition of the ferrous chloride crystals, the gas distributor is buried below the ferrous chloride crystals by about 10cm so as to be convenient for taking out the gas distributor later, the operation can fully discharge the air between crystal grain gaps out of the plastic bag, the situation that the air between ferrous chloride crystal grains is discharged in one process step of vacuumizing is avoided, and the residual air slowly oxidizes the ferrous chloride due to incomplete exhaust.
Furthermore, after the gas distributor is taken out, an external vacuum-pumping machine is used for carrying out vacuum-pumping, nitrogen-filling and sealing operations. During vacuum pumping, the reading of a pressure gauge is ensured to be between-0.08 MPa and-0.1 MPa, and 3-5S is kept, so that air in the package is pumped out as much as possible; when nitrogen is filled, the packaging bag is filled until the packaging bag slightly bulges so as to prevent the sealing bag from being punctured by sharp objects and the ferrous chloride crystal from failing to keep fresh; the hot-melting sealing temperature is 60-80 ℃, and after the hot-melting sealing is finished, alkaline water is needed to be used for checking whether the packaging opening leaks air, so that the sealing performance of the ferrous chloride crystal package is ensured.
In the invention, by improving the production process, the solution contains a small amount of Fe3+Reduction to ensure that the ferrous chloride crystals before packaging are Fe-free3+In the packaging process, air existing among the crystals is removed by means of vacuum pumping through technical means of crushing the agglomerates, the gas distributor and filling with nitrogen, so that the storage time of the packed ferrous chloride crystals is prolonged, the ferrous chloride crystals are in a loose state when the packed ferrous chloride crystals are used, and the use experience of customers is greatly improved.
Detailed Description
Example 1
A packaging method of ferrous chloride crystals comprises the following steps:
s1, adding 0.8kg of reduced iron powder into 1 ton of ferrous chloride hot concentrated solution with 18.6% of Fe and the temperature of 80 ℃, and adding 0.63% of the ferrous chloride solutionFe (b) of3+Reducing until not detected;
s2, filter pressing is carried out while the solution is hot, filtrate is cooled to below 25 ℃, ferrous chloride crystals are separated out through crystallization, and the ferrous chloride crystals are separated from liquid through a centrifugal machine to obtain 0.62 ton of ferrous chloride crystals;
s3, crushing the bonded crystal into uniform single crystal grains by using a lump crusher;
s4, using a hot-melt polypropylene/polyethylene composite film packaging bag, placing a gas distributor connected with nitrogen at the bottom of the packaging bag, filling ferrous chloride crystals to 20kg while filling nitrogen, and taking a gas distribution disc out of the packaging bag;
s5, vacuumizing the packaging bag filled with the ferrous chloride to-0.1 MPa by using an external vacuum-pumping machine, keeping 5S, and filling nitrogen until the packaging bag slightly swells and the temperature of hot-melting sealing is 70 ℃. The seal is checked by alkaline water for no leakage.
The packed ferrous chloride crystals were placed in a warehouse at normal temperature, and the product was checked by opening the package at different times and sampling, the results are as follows:
Figure BDA0003064569350000041
example 2
A packaging method of ferrous chloride crystals comprises the following steps:
s1, adding 1kg of reduced iron powder into 1 ton of ferrous chloride hot concentrated solution with 16.5 percent of Fe and the temperature of 60 ℃, and adding 0.42 percent of Fe in the ferrous chloride solution3+Reducing until not detected;
s2, filter pressing is carried out while the solution is hot, filtrate is cooled to below 15 ℃, ferrous chloride crystals are separated out through crystallization, and the ferrous chloride crystals are separated from liquid through a centrifugal machine to obtain 0.47 ton of ferrous chloride crystals;
s3, crushing the bonded crystal into uniform single crystal grains by using a lump crusher;
s4, using a hot-melt polypropylene/polyethylene composite film packaging bag, placing a gas distributor connected with nitrogen at the bottom of the packaging bag, filling ferrous chloride crystals to 40kg while filling nitrogen, and taking a gas distribution disc out of the packaging bag;
s5, vacuumizing the packaging bag filled with the ferrous chloride to-0.1 MPa by using an external vacuum-pumping machine, keeping 5S, and filling nitrogen until the packaging bag slightly swells and the temperature of hot-melting sealing is 60 ℃. The seal is checked by alkaline water for no leakage.
The packed ferrous chloride crystals were placed in a warehouse at normal temperature, and the product was checked by opening the package at different times and sampling, the results are as follows:
Figure BDA0003064569350000051
example 3
A packaging method of ferrous chloride crystals comprises the following steps:
s1, adding 0.5kg of reduced iron powder into 1 ton of ferrous chloride hot concentrated solution with 20.1% of Fe and the temperature of 90 ℃, and adding 0.74% of Fe in the ferrous chloride solution3+Reducing until not detected;
s2, filter pressing is carried out while the solution is hot, filtrate is cooled to below 20 ℃, ferrous chloride crystals are separated out through crystallization, and the ferrous chloride crystals are separated from liquid through a centrifugal machine to obtain 0.69 ton of ferrous chloride crystals;
s3, crushing the bonded crystal into uniform single crystal grains by using a lump crusher;
s4, using a hot-melt polypropylene/polyethylene composite film packaging bag, placing a gas distributor connected with nitrogen at the bottom of the packaging bag, filling ferrous chloride crystals to 25kg while filling nitrogen, and taking a gas distribution disc out of the packaging bag;
s5, vacuumizing the packaging bag filled with the ferrous chloride to-0.8 MPa by using an external vacuum pump, keeping 5S, filling nitrogen until the packaging bag slightly swells, and carrying out hot melting sealing at the temperature of 80 ℃. The seal is checked by alkaline water for no leakage.
The packed ferrous chloride crystals were placed in a warehouse at normal temperature, and the product was checked by opening the package at different times and sampling, the results are as follows:
Figure BDA0003064569350000061
comparative example 1
The ferrous chloride crystals produced in step S2 of example 1 were packaged in plastic bags and then sealed with simple tape.
Comparative example 2
The ferrous chloride crystals produced in step S2 of example 1 were packed in plastic bags, evacuated, and sealed by hot melting.
Comparative example 3
The ferrous chloride crystals produced in step S2 of example 1 were packed in plastic bags, evacuated, flushed with nitrogen, and sealed by heat-melting.
The ferrous chloride crystals packed in the comparative example were stored in a warehouse under the same conditions as in the examples, and samples were taken at different times to check the product condition, and the results are shown in the following table:
Figure BDA0003064569350000071
from the results of the above examples and comparative examples, it can be seen that: the common fresh-keeping mode of vacuumizing, nitrogen filling and sealing packaging can relatively slow down the oxidation speed of the ferrous chloride, but the preservation effect still cannot meet the requirement of the ferrous chloride for Fe in the electronic industry3+A requirement of < 0.1%. Through the improvement of the packaging process, the air and water vapor existing among the crystals are removed as much as possible by the technical means of crushing the agglomerates, using a gas distributor and filling while filling nitrogen, so that the hermetically packaged ferrous chloride crystals can be stably kept for more than one year.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.

Claims (7)

1. A packaging method of ferrous chloride crystals is characterized by comprising the following steps:
s1, adding reduced iron powder into a ferrous chloride hot concentrated solution with Fe being more than 15%, and adding a small amount of Fe in the ferrous chloride solution3+Reduction;
s2, carrying out filter pressing while the solution is hot, cooling the filtrate, crystallizing to separate out ferrous chloride crystals, and separating the ferrous chloride crystals from the liquid by using a centrifugal machine to obtain ferrous chloride crystals;
s3, using a lump crusher to crush the bonded crystals into single crystal grains with uniform particles;
s4, using a hot-melt plastic packaging bag, placing a gas distributor connected with nitrogen at the bottom of the plastic bag, filling ferrous chloride crystals to the required weight while filling the nitrogen, and taking the gas distribution disc out of the packaging bag;
s5, performing vacuum pumping, nitrogen filling and sealing operation on the filled ferrous chloride by using an external vacuum pumping machine.
2. The method for packaging ferrous chloride crystals as claimed in claim 1 wherein: the mass ratio of the addition amount of the reduced iron powder to the solution in the S1 is 0.5-1: 1000.
3. The method for packaging ferrous chloride crystals as claimed in claim 1 wherein: s4, the method further comprises the step of continuously lifting the gas distributor upwards according to the filling condition of the ferrous chloride crystals, so that the gas distributor is buried 10cm below the solid particles, and the gas distributor is convenient to take out in the following process.
4. The method for packaging ferrous chloride crystals as claimed in claim 1 wherein: in S5, the evacuation conditions were: the reading of the pressure gauge is between-0.08 and-0.1 MPa, and the pressure gauge is kept for 3 to 5 seconds.
5. The method for packaging ferrous chloride crystals as claimed in claim 4, wherein: in S5, the hot-melt sealing temperature is: 60-80 ℃.
6. The method for packaging ferrous chloride crystals as claimed in claim 5, wherein: after S5, the method further comprises using alkaline water to check whether the package opening is air-leakage after the hot-melt sealing is completed.
7. The method for packaging ferrous chloride crystals as claimed in claim 1 wherein: the temperature of the ferrous chloride heat concentrated solution in the S1 is 60-90 ℃.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1224378A (en) * 1968-04-26 1971-03-10 Alberta Res Council A method for converting particulate ferrous chloride to iron
JPH10272301A (en) * 1997-03-31 1998-10-13 Nittetsu Mining Co Ltd Method for treating ferrous compound-containing hydrochloric acid waste solution
CN203345231U (en) * 2013-05-22 2013-12-18 上海垚远科技发展有限公司 Feedback type nitrogen-filled vacuum package machine
CN110950389A (en) * 2019-12-27 2020-04-03 斯瑞尔环境科技股份有限公司 Production process of granular ferrous chloride dihydrate
CN110980833A (en) * 2019-12-16 2020-04-10 斯瑞尔环境科技股份有限公司 Preparation method of electronic-grade ferrous chloride
CN112062164A (en) * 2020-08-25 2020-12-11 斯瑞尔环境科技股份有限公司 Production method of reagent-grade ferric trichloride

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1224378A (en) * 1968-04-26 1971-03-10 Alberta Res Council A method for converting particulate ferrous chloride to iron
JPH10272301A (en) * 1997-03-31 1998-10-13 Nittetsu Mining Co Ltd Method for treating ferrous compound-containing hydrochloric acid waste solution
CN203345231U (en) * 2013-05-22 2013-12-18 上海垚远科技发展有限公司 Feedback type nitrogen-filled vacuum package machine
CN110980833A (en) * 2019-12-16 2020-04-10 斯瑞尔环境科技股份有限公司 Preparation method of electronic-grade ferrous chloride
CN110950389A (en) * 2019-12-27 2020-04-03 斯瑞尔环境科技股份有限公司 Production process of granular ferrous chloride dihydrate
CN112062164A (en) * 2020-08-25 2020-12-11 斯瑞尔环境科技股份有限公司 Production method of reagent-grade ferric trichloride

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