CN1624240A - Purification and decolorization method and process of polyaluminum chloride solution used for paper sizing precipitant - Google Patents
Purification and decolorization method and process of polyaluminum chloride solution used for paper sizing precipitant Download PDFInfo
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- CN1624240A CN1624240A CN 200310115567 CN200310115567A CN1624240A CN 1624240 A CN1624240 A CN 1624240A CN 200310115567 CN200310115567 CN 200310115567 CN 200310115567 A CN200310115567 A CN 200310115567A CN 1624240 A CN1624240 A CN 1624240A
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000008569 process Effects 0.000 title claims abstract description 20
- 238000004513 sizing Methods 0.000 title claims abstract description 19
- 238000000746 purification Methods 0.000 title claims abstract description 7
- 238000004042 decolorization Methods 0.000 title abstract description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 238000004090 dissolution Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims abstract 4
- 229910021645 metal ion Inorganic materials 0.000 claims abstract 2
- 239000000047 product Substances 0.000 claims description 11
- 229910001385 heavy metal Inorganic materials 0.000 claims description 10
- 239000012716 precipitator Substances 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 230000036647 reaction Effects 0.000 claims description 3
- 239000008394 flocculating agent Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 1
- 239000008188 pellet Substances 0.000 claims 1
- 239000008400 supply water Substances 0.000 claims 1
- 238000004065 wastewater treatment Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- RQMIWLMVTCKXAQ-UHFFFAOYSA-N [AlH3].[C] Chemical compound [AlH3].[C] RQMIWLMVTCKXAQ-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
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- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Removal Of Specific Substances (AREA)
Abstract
本发明涉及一种普通聚合氯化铝的纯化脱色方法及工艺，其特征在于：向普通聚合氯化铝溶液中加入铝屑等还原态铝材料，加热升温至一定温度，通过铝的酸性溶解及金属铝表面腐蚀原电池反应，氧化还原溶液中的金属离子及有机杂质，达到纯化脱色的目的，产品可用作造纸施胶沉淀剂。本发明工艺简单，脱色速度快，脱色效率高，操作简便，生产成本低，可有效提高聚合氯化铝的品质。The invention relates to a purification and decolorization method and process of common polyaluminum chloride, which is characterized in that: adding reduced aluminum materials such as aluminum scraps to the common polyaluminum chloride solution, heating to a certain temperature, through the acidic dissolution of aluminum and The metal aluminum surface is corroded by the primary battery reaction, and the metal ions and organic impurities in the redox solution are purified to achieve the purpose of decolorization. The product can be used as a paper sizing and precipitating agent. The invention has the advantages of simple process, fast decolorization speed, high decolorization efficiency, simple operation and low production cost, and can effectively improve the quality of polyaluminum chloride.
Description
Technical Field
The invention relates to a method and a process for purifying and decoloring common polyaluminium chloride flocculating agent, in particular to a method and a process for decoloring polyaluminium chloride used for a papermaking sizing precipitator.
Background
The traditional acidic paper making process adopts dispersed rosin size as sizing agent and aluminum sulfate as sizing precipitator, so that the produced paper has poor whiteness, easy yellowing, easy brittleness, short storage life and poor sizing effect, and is not easy to manufacture high-grade paper. And polyaluminium chloride is adopted to replace aluminum sulfate as a papermaking sizing precipitator, sizing can be carried out under a neutral condition of pH 6.5-7.5, and the produced paper has high whiteness, fine surface, good smoothness, small difference between two surfaces, good glossiness, low yellowing value and high bursting strength, and calcium carbonate with high whiteness, small granularity and low price can be adopted as a papermaking filler. Meanwhile, the neutral sizing by adopting the polyaluminium chloride also has the advantages of reducing equipment corrosion, reducing the dosage of the sizing agent, increasing the retention rate of the sizing agent, accelerating dehydration and the like.
Polyaluminium chloride used in the sizing process for paper manufacture must be colorless or otherwise interfere with the whiteness of the paper and impart color to the paper. At present, the polyaluminium chloride is produced by using various raw materials and production processes in China, and except that a few polyaluminium chloride products prepared by using high-purity raw materials are colorless, most polyaluminium chloride products are produced by using aluminiferous ores, waste aluminium scraps, aluminium slag and byproduct hydrochloric acid, have certain color and cannot be used as a papermaking sizing precipitator. The polyaluminium chloride prepared by the high-purity raw material is expensive, the sizing cost is high, and the polyaluminium chloride is difficult to accept by paper-making manufacturers, so that the popularization and the application of the papermaking process using the polyaluminium chloride as the sizing precipitator in China are limited. Therefore, the practical and feasible process method is adopted to decolor the colored polyaluminium chloride, and the production of cheap and colorless polyaluminium chloride becomes the key for popularizing the papermaking process using the polyaluminium chloride as the sizing precipitator.
The invention provides a simple, convenient, rapid, efficient and economic method and process for purifying and decoloring polyaluminium chloride by adopting the micro-electrolysis principle of aluminic acid solubility and metallic aluminum surface corrosion to meet the requirement.
The purification and decoloration of the solution are mainly to remove or destroy chromophoric groups of inorganic ions, particularly heavy metal ions and organic matters which develop in the solution, and the color in the polyaluminium chloride solution is mainly formed by heavy metal ions, particularly Fe3+、Fe2+The main removal methods include chemical precipitation, chemical reduction, ion exchange, adsorption, electrolysis, and microelectrolysis. Wherein, the chemical precipitation method and the chemical reduction method need to add a precipitator and a reducing agent, the treatment cost is high, and the process is complex; the ion exchange method and the adsorption method have slow decoloring speed, high cost, easy saturation of ion exchange resin and adsorbent and complex regeneration process; the electrolysis method mainly removes color-developing substances by oxidation-reduction reactions occurring on the cathode and anode electrodes when energized, but consumes electric energy and requires a special electrolysis facilityThe power supply facilities and the formed electrode materials have high operating cost; the micro-electrolysis method is characterized in that substances with different oxidation-reduction potentials are subjected to primary cell reaction in an electrolyte solution, and chromogenic substances are removed by utilizing the oxidation-reduction reaction of a cathode and an anode of the primary cell. Chinese patent CN1277940 discloses a method for removing heavy metal ions and organic matters in polyaluminium chloride prepared by the reaction of high-alumina ash and waste acid by using an aluminum-carbon micro-electrolysis bed. The process needs additional active carbon, increases the production cost, carries out micro-electrolysis reaction at normal temperature, and has slow removal speed of heavy metals and organic matters and long reaction time.
Disclosure of Invention
The invention aims to provide a simple, convenient, quick, efficient and economic purification and decoloration method and process for polyaluminium chloride.
The invention adds aluminum scraps, aluminum ingots, aluminum slag, aluminum wires and the like into common polyaluminium chloride for reductionThe heavy metal and organic impurities, especially Fe, in the polyaluminium chloride solution are removed by redox of the cathode and the anode by utilizing the acid dissolution of aluminum and the surface corrosion of metallic aluminum in the galvanic cell reaction at high temperature3+、Fe2+So as to achieve the purpose of decoloring. The reaction mechanism is as follows: when aluminum scraps and the like are added to the acidic polyaluminum chloride electrolyte, the surfaces of the aluminum scraps dissolve due to acidity, and Fe in the solution3+、Fe2+The heavy metal ions are reduced on the surface of the aluminum scraps and deposited on the surface of the aluminum scraps, so that the potential of a local electrode on the surface of the aluminum scraps is unbalanced, countless corrosion primary batteries are formed, and aluminum is dissolved in the anode of each primary battery; galvanic cellCathode of (H)+And other heavy metal ions are reduced and deposited, and meanwhile, organic matters in the solution are reduced or oxidized on the surface of the aluminum scraps or are newly generated by H in the solution2And (4) reducing.
Aluminum acid dissolution:
anode:
cathode: (M is a metal simple substance)
The polyaluminium chloride raw material adopted by the invention can be a product produced by various methods, and the chromaticity of the polyaluminium chloride is not limited.
The added substances containing reduced aluminum can be aluminum scraps, aluminum ingots, aluminum wires and aluminum particles, the aluminum consumed by dissolution can improve the concentration of total aluminum in the polyaluminum chloride solution, the basicity of the product is improved by 1.0-2.0%, and the undissolved aluminum scraps can be washed by acidic water to remove heavy metals deposited on the surface of the aluminum scraps and then recycled.
The method for improving the temperature of the polyaluminium chloride solution can greatly accelerate the decolorization rate, wherein the higher the temperature is, the faster the decolorization rate is, and the shorter the decolorization time is, the temperature range is 15-80 ℃, and the optimal temperature range is 60-70 ℃.
Because most of the production of the polyaluminium chloride is carried out at the temperature of more than 50 ℃, the high-temperature decolorization process adopted by the invention only needs to add a decolorization reaction tank after the hot filtration process of the polyaluminium chloride production, and the decolorized solution is filtered again, and no additional heating process is needed, so the energy consumption is low, and the operation is simple.
The decolorized polyaluminum chloride is filtered, the solution is colorless transparent liquid, the chroma is below 15 ℃, and the decolorization rate is more than 95%.
The invention is further illustrated by the following examples:
example 1:
taking 300ml of a commercial polyaluminum chloride solution with the chroma of 400 ℃, placing the commercial polyaluminum chloride solution in a 500ml beaker, adding 5g of aluminum scraps, covering a watch glass, placing the watch glass in a 70 ℃ water bath for heating for 40min, filtering the solution to obtain a filtrate, namely a required product, and washing the residual aluminum scraps with acidic water for recycling. The chromaticity of the polyaluminium chloride solution before and after decolorization is measured by adopting a platinum-cobalt visual colorimetry, the content of metal elements is measured by adopting ICP-AES, the total aluminium and basicity are measured by adopting a chemical titration method, and the results are as follows:
| detecting items | Before decolorization | After decolorization |
| Chroma (degree) | 400 | 15 |
| Al2O3Content% | 11.22 | 11.70 |
| Degree of basicity% | 65.70 | 67.97 |
| Cd (mg/L) | 0.001 | 0.001 |
| Cr (mg/L) | 0.94 | 0.90 |
| Cu (mg/L) | 0.63 | 0.18 |
| Fe (mg/L) | 858.55 | 156.26 |
| Mn (mg/L) | 1.15 | 1.08 |
| Ni (mg/L) | 0.12 | 0.064 |
| Pb (mg/L) | 0.05 | 0.10 |
| Zn (mg/L) | 0.80 | 0.85 |
| Al (mg/L) | 70995 | 78168 |
Example 2:
300ml of a commercially available polyaluminum chloride solution having a chroma of 400 ℃ was taken and placed in a 500ml beakerIn the cup, 5g of aluminum scraps were added, and the cup was covered with a watchAnd (3) making the mixture react for 24 hours at room temperature of 22 ℃ in a dish, then filtering the solution to obtain filtrate, namely the required product, and washing the residual aluminum scraps with acidic water for recycling. The chromaticity of the polyaluminium chloride solution before and after decolorization is measured by a platinum-cobalt visual colorimetry, the total aluminum and basicity are measured by a chemical titration method, and the results are as follows:
| detecting items | Before decolorization | After decolorization |
| Chroma (degree) | 400 | 15 |
| Al2O3Content% | 11.22 | 13.73 |
| Degree of basicity% | 65.70 | 66.28 |
The above examples show that the invention has the advantages of high decoloring speed, high efficiency, simple process, good removal effect on heavy metal impurities in the polyaluminium chloride solution, improvement of the total aluminum content and basicity of the product, improvement of the product grade and good industrial popularization and application value.
In the drawings: 1 is polyaluminium chloride solution before decolorization, and 2 is polyaluminium chloride solution after decolorization.
Claims (4)
1. A method and a process for purifying and decoloring polyaluminium chloride used for a papermaking sizing precipitator are characterized in that: adding reduced aluminum materials such as aluminum scraps and the like into a common polyaluminium chloride solution, heating to a certain temperature, oxidizing metal ions and organic impurities in the reduction solution through acidic dissolution of aluminum and corrosion of the surface of metal aluminum on a galvanic cell reaction, and filtering after a certain period of reaction to obtain a filtrate,namely a high-purity transparent colorless polyaluminium chloride product.
2. The reduced aluminum material according to claim 1, characterized in that: it may be aluminum scrap, aluminum pellets, aluminum ingots, aluminum wire, aluminum sheet, or a mixture of these materials.
3. The heating reaction temperature and reaction time according to claim 1, wherein: the reaction temperature is 15-80 ℃, the optimal temperature is 60-70 ℃, the reaction time is reduced along with the rise of the temperature, and the reaction time is 40 min-24 hr.
4. The polyaluminum chloride solution produced by the purification and decoloration method and the process according to claim 1, which is characterized in that: the color intensity of the decolored polyaluminium chloride product is less than 15 degrees, the decoloration rate is more than 95 percent, the heavy metal content is obviously reduced, and the polyaluminium chloride product can be used as a papermaking sizing precipitator and can also be applied to purification and impurity removal of a polyaluminium chloride flocculating agent in water supply and wastewater treatment.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101155675A CN1312357C (en) | 2003-12-02 | 2003-12-02 | Purification decolouring method of poly aluminium chloride solution used for paper making sizing precipitant and its technology |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101155675A CN1312357C (en) | 2003-12-02 | 2003-12-02 | Purification decolouring method of poly aluminium chloride solution used for paper making sizing precipitant and its technology |
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| Publication Number | Publication Date |
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| CN1624240A true CN1624240A (en) | 2005-06-08 |
| CN1312357C CN1312357C (en) | 2007-04-25 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107503234A (en) * | 2017-08-18 | 2017-12-22 | 首都博物馆 | A kind of neutral aluminium salt sizing precipitant and preparation method and application |
| CN113828014A (en) * | 2021-09-14 | 2021-12-24 | 海南金海浆纸业有限公司 | Purification and decoloration process of polyaluminium chloride solution |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4108972C2 (en) * | 1991-03-20 | 1995-08-17 | Air Lippewerk Recycling Gmbh | Process for increasing the molar aluminum / chlorine ratio in polyaluminum chloride solutions |
| CN1114563C (en) * | 2000-06-15 | 2003-07-16 | 凯米沃特(宜兴)净化剂有限公司 | Method for purifying aluminium-poly-chloride using aluminium-carbon microeletrolysis |
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2003
- 2003-12-02 CN CNB2003101155675A patent/CN1312357C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107503234A (en) * | 2017-08-18 | 2017-12-22 | 首都博物馆 | A kind of neutral aluminium salt sizing precipitant and preparation method and application |
| CN113828014A (en) * | 2021-09-14 | 2021-12-24 | 海南金海浆纸业有限公司 | Purification and decoloration process of polyaluminium chloride solution |
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