CN115821630B - Preparation method of polyaluminium salt sizing agent - Google Patents
Preparation method of polyaluminium salt sizing agent Download PDFInfo
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- CN115821630B CN115821630B CN202211529274.0A CN202211529274A CN115821630B CN 115821630 B CN115821630 B CN 115821630B CN 202211529274 A CN202211529274 A CN 202211529274A CN 115821630 B CN115821630 B CN 115821630B
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- 238000004513 sizing Methods 0.000 title claims abstract description 102
- 150000003839 salts Chemical class 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 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 claims abstract description 107
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 96
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 81
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000012065 filter cake Substances 0.000 claims abstract description 23
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 14
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 14
- 239000013065 commercial product Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002351 wastewater Substances 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 239000000123 paper Substances 0.000 description 20
- 239000011734 sodium Substances 0.000 description 12
- 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 9
- 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 9
- 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 9
- 230000000052 comparative effect Effects 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 7
- -1 compound aluminum salt Chemical class 0.000 description 7
- 238000010030 laminating Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000004220 aggregation Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 6
- 239000012629 purifying agent Substances 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000011087 paperboard Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
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- 239000000835 fiber Substances 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical group 0.000 description 1
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Abstract
The invention belongs to the technical field of sizing agents for acid sizing processes in the papermaking industry, and particularly relates to a preparation method of a polyaluminium salt sizing agent. Adding the first aluminum sulfate solution into a reaction kettle, heating to 50-80 ℃ under stirring, dropwise adding a NaOH solution for reaction for 1.5-1.8 hours, then filtering to remove a sodium sulfate solution, and taking a filter cake for later use; adding the second aluminum sulfate solution into a reaction kettle, adding a filter cake under stirring, heating to 95-115 ℃, reacting for 1-1.5 hours, completely dissolving, and adding a phosphoric acid solution to prepare the polyaluminium salt sizing agent. The polyaluminium salt sizing agent prepared by the preparation method disclosed by the invention not only can reduce the discharge of sulfate radical, but also can reduce the total salt discharge in the wastewater discharge by 20-30% on the premise of ensuring the sizing effect, thereby meeting the wastewater discharge standard.
Description
Technical Field
The invention belongs to the technical field of sizing agents for acid sizing processes in the papermaking industry, and particularly relates to a preparation method of a polyaluminium salt sizing agent.
Background
Sizing paper is one of the important ways to significantly increase the added value of paper. The printing adaptability of the paper and the paperboard can be improved by carrying out surface sizing on the paper and the paperboard, the surface strength is increased, the paper and the paperboard have certain resistance to hair and powder falling, the internal bonding degree, the folding strength and the IGT (IGT) napping speed are improved, the air permeability is reduced, the stiffness and the smoothness are improved, and the paper is improved in fat resistance, oil resistance or water resistance and the like.
Rosin-type emulsion sizing agents refer to compositions obtained by emulsifying rosin-type substances in the presence of various emulsifiers and water. The paper obtained using this rosin-type emulsion sizing agent exhibits a good sizing effect due to the emulsion particles fixed to the pulp fibers. Conventionally, as rosin-based materials, so-called reinforced rosin and its esters, in which raw rosin such as gum rosin, tall oil rosin, wood rosin and the like is modified with α, β -unsaturated carboxylic acid such as maleic acid, have been highly appreciated from the viewpoint of their excellent sizing properties.
At present, when a rosin type emulsion sizing agent is used, aluminum sulfate or a compound aluminum salt sizing agent (for example, a compound aluminum salt sizing promoter described in patent CN 112095362B) is inevitably added for sizing, and although both can improve the sizing effect of the surface sizing agent, sulfate emission is easily out of standard after aluminum sulfate is added, and the compound aluminum salt sizing agent is adopted for sizing, only the sulfate emission index is reduced, but the emission of the total salt index in wastewater is still out of standard.
Disclosure of Invention
The purpose of the invention is that: a method for preparing a polyaluminium salt sizing agent is provided. The polyaluminium salt sizing agent prepared by the preparation method provided by the invention not only can reduce the sulfate radical content in the wastewater, but also can enable the total salt discharge in the wastewater to reach the standard.
The preparation method of the polyaluminium salt sizing agent provided by the invention comprises the following steps:
(1) Adding the first aluminum sulfate solution into a reaction kettle, heating to 50-80 ℃ under stirring, dropwise adding a NaOH solution for reaction for 1.5-1.8 hours, then filtering to remove a sodium sulfate solution, and taking a filter cake for later use;
(2) Adding the second aluminum sulfate solution into a reaction kettle, adding the filter cake prepared in the step (1) under the stirring condition, heating to 95-115 ℃, reacting for 1-1.5 hours, and adding the phosphoric acid solution after the second aluminum sulfate solution is completely dissolved to prepare the polyaluminium salt sizing agent.
Wherein:
the first aluminum sulfate solution in the step (1) is prepared by mixing a liquid aluminum sulfate solution with water, wherein the mass ratio of the liquid aluminum sulfate solution to the water is 1:1.5; the liquid aluminum sulfate solution is a commercial product, wherein Al 2 O 3 The content is 7.5-8%.
The first aluminum sulfate solution in the step (1) adopts Al in the liquid aluminum sulfate solution during preparation 2 O 3 The content is 7.5-8%; the liquid aluminum sulfate solution and water are mixed according to the mass ratio of 1:1.5 so as to reduce Al in the liquid aluminum sulfate solution 2 O 3 The content of (2) is reduced from 7.5-8% to 3-3.2%. The purpose of this is to: firstly, in order to promote the reaction to be carried out stably and avoid the phenomenon of sudden aggregation, and secondly, in order to reduce the generated Na 2 SO 4 In such a way that Na is easily dissolved in the next step 2 SO 4 Solution from soluble Al (OH) 3 Separated out.
The mass concentration of the sodium hydroxide solution in the step (1) is 13.57%.
The molar ratio of the first aluminum sulfate solution to the sodium hydroxide solution in the step (1) is 1:6.
And (3) recycling the sodium sulfate solution in the step (1) for producing the aluminum sulfate water purifying agent.
The chemical reaction occurring in step (1) is:
the second aluminum sulfate solution in the step (2) is a commercial liquid aluminum sulfate solution, wherein Al 2 O 3 The content is 7.5-8%.
The mass ratio of the second aluminum sulfate solution to the filter cake in the step (2) is 0.75-0.65:0.25-0.35.
The mass concentration of the phosphoric acid solution in the step (2) is 85%, and the addition amount of the phosphoric acid is 1-1.05% of the mass of the prepared polyaluminium salt sizing agent.
The chemical reaction equation occurring in step (2) is shown below:
wherein n is more than or equal to 1 and less than or equal to 5, and m is less than 10.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method of the polyaluminium salt sizing agent has the advantages that the technological parameters are easy to control, and the prepared polyaluminium salt sizing agent has excellent performance.
(2) The polyaluminium salt sizing agent prepared by the preparation method disclosed by the invention can reduce the discharge of sulfate radical and the discharge of total salt in wastewater discharge by 20-30% on the premise of ensuring the sizing effect, so that the wastewater discharge standard is reached; in addition, the polyaluminium salt sizing agent has a longer molecular chain, the polymerization degree is up to 45-54%, and the sizing dosage can be reduced by more than 30%.
Detailed Description
The invention is further described below with reference to examples.
Example 1
The method for preparing the polyaluminum salt sizing agent in the embodiment 1 comprises the following steps:
(1) Adding the first aluminum sulfate solution into a reaction kettle, heating to 65 ℃ under stirring, dropwise adding a NaOH solution for reaction for 1.7 hours, filtering to remove a sodium sulfate solution, and taking a filter cake for later use;
(2) And (3) adding the second aluminum sulfate solution into a reaction kettle, adding the filter cake prepared in the step (1) under the stirring condition, heating to 105 ℃, reacting for 1.3 hours, completely dissolving, and adding a phosphoric acid solution to prepare the polyaluminium salt sizing agent.
Wherein:
the first aluminum sulfate solution in the step (1) is prepared by mixing a liquid aluminum sulfate solution with water, wherein the mass ratio of the liquid aluminum sulfate solution to the water is 1:1.5; the liquid aluminum sulfate solution is a commercial product, wherein Al 2 O 3 The content was 7.8%.
The first aluminum sulfate solution in the step (1) adopts Al in the liquid aluminum sulfate solution during preparation 2 O 3 The content is 7.8%; the liquid aluminum sulfate solution and water are mixed according to the mass ratio of 1:1.5 so as to reduce Al in the liquid aluminum sulfate solution 2 O 3 The content of (2) is reduced from 7.8% to 3.12%. The purpose of this is to: firstly, in order to promote the reaction to be carried out stably and avoid the phenomenon of sudden aggregation, and secondly, in order to reduce the generated Na 2 SO 4 In such a way that Na is easily dissolved in the next step 2 SO 4 Solution from soluble Al (OH) 3 Separated out.
The mass concentration of the sodium hydroxide solution in the step (1) is 13.57%; namely, 50g of sodium hydroxide (the mass content is 95% calculated as NaOH) is dissolved in 300g of water.
The molar ratio of the first aluminum sulfate solution to the sodium hydroxide solution in the step (1) is 1:6.
And (3) recycling the sodium sulfate solution in the step (1) for producing the aluminum sulfate water purifying agent.
The chemical reaction occurring in step (1) is:
the second aluminum sulfate solution in the step (2) is a commercial liquid aluminum sulfate solution, wherein Al 2 O 3 The content was 7.8%.
The mass ratio of the second aluminum sulfate solution to the filter cake in the step (2) is 0.65:0.35.
The mass concentration of the phosphoric acid solution in the step (2) is 85%, and the addition amount of the phosphoric acid is 1% of the mass of the prepared polyaluminium salt sizing agent.
The chemical reaction equation occurring in step (2) is shown below:
wherein n is more than or equal to 1 and less than or equal to 5, and m is less than 10.
The hydroxyl content of the polyaluminum salt sizing agent prepared in example 1 was detected by chemical titration, the degree of polymerization of the polyaluminum salt sizing agent prepared in example 1 was 54.1%, and the sizing agent solution prepared was clear.
Example 2
The preparation method of the polyaluminum salt sizing agent in the embodiment 2 comprises the following steps:
(1) Adding the first aluminum sulfate solution into a reaction kettle, heating to 50 ℃ under stirring, dropwise adding a NaOH solution for reaction for 1.8 hours, filtering to remove a sodium sulfate solution, and taking a filter cake for later use;
(2) And (3) adding the second aluminum sulfate solution into a reaction kettle, adding the filter cake prepared in the step (1) under the stirring condition, heating to 95 ℃, reacting for 1.5 hours, completely dissolving, and adding a phosphoric acid solution to prepare the polyaluminium salt sizing agent.
Wherein:
the first aluminum sulfate solution in the step (1) is prepared by mixing a liquid aluminum sulfate solution with water, wherein the mass ratio of the liquid aluminum sulfate solution to the water is 1:1.5; the liquid aluminum sulfate solution is a commercial product, wherein Al 2 O 3 The content was 7.8%.
The first aluminum sulfate solution in the step (1) adopts Al in the liquid aluminum sulfate solution during preparation 2 O 3 The content is 7.8%; the liquid aluminum sulfate solution and water are mixed according to the mass ratio of 1:1.5 so as to reduce Al in the liquid aluminum sulfate solution 2 O 3 The content of (2) is reduced from 7.8% to 3.12%. The purpose of this is to: firstly, in order to promote the reaction to be carried out stably and avoid the phenomenon of sudden aggregation, and secondly, in order to reduce the generated Na 2 SO 4 In such a way that Na is easily dissolved in the next step 2 SO 4 Solution from soluble Al (OH) 3 Separated out.
The mass concentration of the sodium hydroxide solution in the step (1) is 13.57%; namely, 50g of sodium hydroxide (the mass content is 95% calculated as NaOH) is dissolved in 300g of water.
The molar ratio of the first aluminum sulfate solution to the sodium hydroxide solution in the step (1) is 1:6.
And (3) recycling the sodium sulfate solution in the step (1) for producing the aluminum sulfate water purifying agent.
The chemical reaction occurring in step (1) is:
the second aluminum sulfate solution in the step (2) is a commercial liquid aluminum sulfate solution, wherein Al 2 O 3 The content was 7.8%.
The mass ratio of the second aluminum sulfate solution to the filter cake in the step (2) is 0.70:0.30.
The mass concentration of the phosphoric acid solution in the step (2) is 85%, and the addition amount of the phosphoric acid is 1% of the mass of the prepared polyaluminium salt sizing agent.
The chemical reaction equation occurring in step (2) is shown below:
wherein n is more than or equal to 1 and less than or equal to 5, and m is less than 10.
The hydroxyl content in the polyaluminum salt sizing agent prepared in example 2 was detected by chemical titration, the degree of polymerization of the polyaluminum salt sizing agent prepared in example 2 was 49.7%, and the sizing agent solution prepared was clear.
Example 3
The preparation method of the polyaluminum salt sizing agent in the embodiment 3 comprises the following steps:
(1) Adding the first aluminum sulfate solution into a reaction kettle, heating to 80 ℃ under stirring, dropwise adding a NaOH solution for reaction for 1.5 hours, filtering to remove a sodium sulfate solution, and taking a filter cake for later use;
(2) And (3) adding the second aluminum sulfate solution into a reaction kettle, adding the filter cake prepared in the step (1) under the stirring condition, heating to 115 ℃, reacting for 1.0 hour, completely dissolving, and adding a phosphoric acid solution to prepare the polyaluminium salt sizing agent.
Wherein:
the first aluminum sulfate solution in the step (1) is prepared by mixing a liquid aluminum sulfate solution with water, wherein the mass ratio of the liquid aluminum sulfate solution to the water is 1:1.5; the liquid aluminum sulfate solution is a commercial product, wherein Al 2 O 3 The content was 7.8%.
The first aluminum sulfate solution in the step (1) adopts Al in the liquid aluminum sulfate solution during preparation 2 O 3 The content is 7.8%; the liquid aluminum sulfate solution and water are mixed according to the mass ratio of 1:1.5 so as to reduce Al in the liquid aluminum sulfate solution 2 O 3 The content of (2) is reduced from 7.8% to 3.12%. The purpose of this is to: firstly, in order to promote the reaction to be carried out stably and avoid the phenomenon of sudden aggregation, and secondly, in order to reduce the generated Na 2 SO 4 In such a way that Na is easily dissolved in the next step 2 SO 4 Solution from soluble Al (OH) 3 Separated out.
The mass concentration of the sodium hydroxide solution in the step (1) is 13.57%; namely, 50g of sodium hydroxide (the mass content is 95% calculated as NaOH) is dissolved in 300g of water.
The molar ratio of the first aluminum sulfate solution to the sodium hydroxide solution in the step (1) is 1:6.
And (3) recycling the sodium sulfate solution in the step (1) for producing the aluminum sulfate water purifying agent.
The chemical reaction occurring in step (1) is:
the second aluminum sulfate solution in the step (2) is a commercial liquid aluminum sulfate solution, wherein Al 2 O 3 The content was 7.8%.
The mass ratio of the second aluminum sulfate solution to the filter cake in the step (2) is 0.75:0.25.
The mass concentration of the phosphoric acid solution in the step (2) is 85%, and the addition amount of the phosphoric acid is 1.05% of the mass of the prepared polyaluminium salt sizing agent.
The chemical reaction equation occurring in step (2) is shown below:
wherein n is more than or equal to 1 and less than or equal to 5, and m is less than 10.
The hydroxyl content in the polyaluminum salt sizing agent prepared in example 3 was detected by chemical titration, the degree of polymerization of the polyaluminum salt sizing agent prepared in example 3 was 45.2%, and the sizing agent solution prepared was clear.
Comparative example 1
The preparation method of the polyaluminum salt sizing agent in the comparative example 1 comprises the following steps:
(1) Adding the first aluminum sulfate solution into a reaction kettle, heating to 65 ℃ under stirring, dropwise adding a NaOH solution for reaction for 1.7 hours, filtering to remove a sodium sulfate solution, and taking a filter cake for later use;
(2) And (3) adding the second aluminum sulfate solution into a reaction kettle, adding the filter cake prepared in the step (1) under the stirring condition, heating to 105 ℃, reacting for 1.3 hours, completely dissolving, and adding a phosphoric acid solution to prepare the polyaluminium salt sizing agent.
Wherein:
the first aluminum sulfate solution in the step (1) is prepared by mixing a liquid aluminum sulfate solution with water, wherein the mass ratio of the liquid aluminum sulfate solution to the water is 1:1.5; the liquid aluminum sulfate solution is a commercial product, wherein Al 2 O 3 The content was 7.8%.
The first aluminum sulfate solution in the step (1) adopts Al in the liquid aluminum sulfate solution during preparation 2 O 3 The content is 7.8%; the liquid aluminum sulfate solution and water are mixed according to the mass ratio of 1:1.5 so as to reduce Al in the liquid aluminum sulfate solution 2 O 3 The content of (2) is reduced from 7.8% to 3.12%. The purpose of this is to: firstly, in order to promote the reaction to be carried out stably and avoid the phenomenon of sudden aggregation, and secondly, in order to reduce the generated Na 2 SO 4 In such a way that Na is easily dissolved in the next step 2 SO 4 Solution from soluble Al (OH) 3 Separated out.
The mass concentration of the sodium hydroxide solution in the step (1) is 13.57%; namely, 50g of sodium hydroxide (the mass content is 95% calculated as NaOH) is dissolved in 300g of water.
The molar ratio of the first aluminum sulfate solution to the sodium hydroxide solution in the step (1) is 1:6.
And (3) recycling the sodium sulfate solution in the step (1) for producing the aluminum sulfate water purifying agent.
The chemical reaction occurring in step (1) is:
the second aluminum sulfate solution in the step (2) is a commercial liquid aluminum sulfate solution, wherein Al 2 O 3 The content was 7.8%.
The mass ratio of the second aluminum sulfate solution to the filter cake in the step (2) is 0.9:0.1.
The mass concentration of the phosphoric acid solution in the step (2) is 85%, and the addition amount of the phosphoric acid is 1.2% of the mass of the prepared polyaluminium salt sizing agent.
The hydroxyl content in the polyaluminum salt sizing agent prepared in comparative example 1 was detected by chemical titration, the polymerization degree of the polyaluminum salt sizing agent prepared in comparative example 1 was 35%, and the prepared sizing agent solution was clear. Since the polymerization degree of the polyaluminum salt sizing agent is low, al in the polyaluminum salt sizing agent 3+ The content is low. When applied, al 3+ The binding degree of ions with anionic rosin size is low, resulting in a decrease in sizing properties.
Comparative example 2
The preparation method of the polyaluminum salt sizing agent in the comparative example 2 comprises the following steps:
(1) Adding the first aluminum sulfate solution into a reaction kettle, heating to 65 ℃ under stirring, dropwise adding a NaOH solution for reaction for 1.7 hours, filtering to remove a sodium sulfate solution, and taking a filter cake for later use;
(2) And (3) adding the second aluminum sulfate solution into a reaction kettle, adding the filter cake prepared in the step (1) under the stirring condition, heating to 105 ℃, reacting for 1.3 hours, completely dissolving, and adding a phosphoric acid solution to prepare the polyaluminium salt sizing agent.
Wherein:
the first aluminum sulfate solution in the step (1) is prepared by mixing a liquid aluminum sulfate solution with water, wherein the mass ratio of the liquid aluminum sulfate solution to the water is 1:1.5; the liquid aluminum sulfate solution is a commercial product, wherein Al 2 O 3 The content was 7.8%.
The first aluminum sulfate solution in the step (1) adopts Al in the liquid aluminum sulfate solution during preparation 2 O 3 The content is 7.8%; the liquid aluminum sulfate solution and water are mixed according to the mass ratio of 1:1.5 so as to reduce Al in the liquid aluminum sulfate solution 2 O 3 The content of (2) is reduced from 7.8% to 3.12%. The purpose of this is to: firstly, in order to promote the reaction to be carried out stably and avoid the phenomenon of sudden aggregation, and secondly, in order to reduce the generated Na 2 SO 4 In such a way that Na is easily dissolved in the next step 2 SO 4 Solution from soluble Al (OH) 3 Separated out.
The mass concentration of the sodium hydroxide solution in the step (1) is 13.57%; namely, 50g of sodium hydroxide (the mass content is 95% calculated as NaOH) is dissolved in 300g of water.
The molar ratio of the first aluminum sulfate solution to the sodium hydroxide solution in the step (1) is 1:6.
And (3) recycling the sodium sulfate solution in the step (1) for producing the aluminum sulfate water purifying agent.
The chemical reaction occurring in step (1) is:
the second aluminum sulfate solution in the step (2) is a commercial liquid aluminum sulfate solution, wherein Al 2 O 3 The content was 7.8%.
The mass ratio of the second aluminum sulfate solution to the filter cake in the step (2) is 0.55:0.45.
The mass concentration of the phosphoric acid solution in the step (2) is 85%, and the addition amount of the phosphoric acid is 1.0% of the mass of the prepared polyaluminium salt sizing agent.
The chemical reaction equation occurring in step (2) is shown below:
wherein n is more than or equal to 1 and less than or equal to 5, and m is less than 10.
The hydroxyl content in the polyaluminum salt sizing agent prepared in comparative example 2 was detected by chemical titration, the polymerization degree of the polyaluminum salt sizing agent prepared in comparative example 2 was 63.2%, and the prepared sizing agent solution was turbid, and the occurrence of turbidity indicates the presence of Al (OH) which was not dissolved by the aluminum sulfate solution 3 Precipitation occurs during production and application, thereby reducing Al 3+ Binding of ions to anionic rosin size.
The performance test is carried out on the polyaluminium salt sizing agent prepared in the embodiment 1, the sizing effect of the polyaluminium salt sizing agent for sizing is verified, and whether the polyaluminium salt sizing agent meets the sizing requirement of common laminating base paper or not is tested, the content of total salt in wastewater discharge can be reduced, the popularization and the application of the polyaluminium salt sizing agent are finally achieved, and the discharge of the total salt in wastewater can reach the standard.
The method comprises the steps of (1) brushing and loading a polymeric aluminum salt sizing agent on a 1400# paper machine for 2022, taking a water sample for drainage of a workshop ditch every 4 hours from the next morning, and sampling until the polymeric aluminum salt sizing agent is used up. And (3) conveying the water sample to an environmental protection laboratory at any time to detect the total salt content and sulfate ion content in the water sample. Under the condition of the same process control and the same loose glue adding amount, the experiment compares the glue applying effect of the compound aluminum salt sizing agent (the compound aluminum salt sizing agent prepared in the embodiment 1 in the CN112095362B patent) with the reducing condition of the total salt content and the sulfate ion content in the drainage of the workshop trench. The sizing effect of the polyaluminium salt sizing agent was determined.
Adding points: according to the acid sizing process of the base paper, the adding points are the paper machine surface layer, the core layer and the bottom layer pre-papermaking pond, which are the same as the adding process of the composite aluminum salt sizing agent for workshops.
Using a polyaluminum salt sizing agent (prepared in example 1 of the present invention) and a composite aluminum salt sizing agent (composite aluminum salt sizing agent prepared in example 1 of the CN112095362B patent), the list of values for detection of drainage, total salt content and sulfate ion content in the workshop was as follows:
table 1 water sample test results
Analysis:
according to the detection of the waste water emission samples in the environment-friendly laboratory, the detection results of the total salt content and the sulfate ion content show that the sulfate ion content is basically the same by using the polyaluminium salt sizing agent and the compound aluminum salt sizing agent, but the total salt content of the waste water emission is obviously reduced by using the polyaluminium salt sizing agent.
Using a composite aluminum salt sizing agent:
240g/m 2 the average waste water discharge total salt content of the common laminating base paper is as follows: 1232mg/L;
320g/m 2 the average waste water discharge total salt content of the common laminating base paper is as follows: 1316mg/L;
390g/m 2 the average waste water discharge total salt content of the common laminating base paper is as follows: 1502mg/L;
320g/m 2 the average waste water discharge total salt content of the common single-sided double-coated base paper is as follows: 1228mg/L;
and a polyaluminium salt sizing agent is used:
240g/m 2 the average waste water discharge total salt content of the common laminating base paper is as follows: 1029.12mg/L;
320g/m 2 the average waste water discharge total salt content of the common laminating base paper is as follows: 1001.0mg/L;
390g/m 2 the average waste water discharge total salt content of the common laminating base paper is as follows: 1126.5mg/L;
320g/m 2 the average waste water discharge total salt content of the common single-sided double-coated base paper is as follows: 1016.45mg/L.
Conclusion:
production pilot scale tests show that the base paper sizing agent added with the polyaluminium salt sizing agent can replace 100% of the compound aluminum salt sizing agent, the same sizing effect can be achieved, and the total salt content is obviously reduced and the average amplitude reduction is between 20% and 30% by measuring the drainage and sampling of waste water in a pilot plant using the polyaluminium salt sizing agent in an environment-friendly laboratory.
Claims (3)
1. A preparation method of a polyaluminium salt sizing agent is characterized by comprising the following steps: the method comprises the following steps:
(1) Adding the first aluminum sulfate solution into a reaction kettle, heating to 50-80 ℃ under stirring, dropwise adding a NaOH solution for reaction for 1.5-1.8 hours, then filtering to remove a sodium sulfate solution, and taking a filter cake for later use;
(2) Adding the second aluminum sulfate solution into a reaction kettle, adding the filter cake prepared in the step (1) under the stirring condition, heating to 95-115 ℃, reacting for 1-1.5 hours, and adding a phosphoric acid solution after the second aluminum sulfate solution is completely dissolved to prepare a polyaluminium salt sizing agent;
wherein:
the first aluminum sulfate solution in the step (1) is prepared by mixing a liquid aluminum sulfate solution with water, wherein the mass ratio of the liquid aluminum sulfate solution to the water is 1:1.5; the liquid aluminum sulfate solution is a commercial product, wherein Al 2 O 3 The content is 7.5% -8%;
the second aluminum sulfate solution in the step (2) is a commercial liquid aluminum sulfate solution, wherein Al 2 O 3 The content is 7.5% -8%;
the mass ratio of the second aluminum sulfate solution to the filter cake in the step (2) is 0.75-0.65:0.25-0.35;
the mass concentration of the phosphoric acid solution in the step (2) is 85%, and the addition amount of the phosphoric acid is 1% -1.05% of the mass of the prepared polyaluminium salt sizing agent.
2. The method for preparing the polyaluminum salt sizing agent according to claim 1, wherein: the mass concentration of the sodium hydroxide solution in the step (1) is 13.57%.
3. The method for preparing the polyaluminum salt sizing agent according to claim 1, wherein: the molar ratio of the first aluminum sulfate solution to the sodium hydroxide solution in the step (1) is 1:6.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB190112769A (en) * | 1901-06-22 | 1902-05-08 | Casimir Wurster | An Improvement in Sizing Paper. |
| US4563342A (en) * | 1982-11-02 | 1986-01-07 | Boliden Aktibolag | Method for producing basic aluminum sulphate (III) |
| CN102493273A (en) * | 2011-11-19 | 2012-06-13 | 山东轻工业学院 | Alkenyl succinic anhydride emulsion sizing agent and its preparation method |
| CN105712387A (en) * | 2016-03-15 | 2016-06-29 | 北京世纪地和控股有限公司 | Method for preparing aluminum hydroxide sulfate |
| CN115075051A (en) * | 2021-03-12 | 2022-09-20 | 荒川化学工业株式会社 | Rosin sizing agent for papermaking and paper |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE526891C2 (en) * | 2002-07-09 | 2005-11-15 | Feralco Ab | Aluminum sulfate compositions containing polynuclear complexes and process for their preparation and use thereof |
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- 2022-11-30 CN CN202211529274.0A patent/CN115821630B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB190112769A (en) * | 1901-06-22 | 1902-05-08 | Casimir Wurster | An Improvement in Sizing Paper. |
| US4563342A (en) * | 1982-11-02 | 1986-01-07 | Boliden Aktibolag | Method for producing basic aluminum sulphate (III) |
| CN102493273A (en) * | 2011-11-19 | 2012-06-13 | 山东轻工业学院 | Alkenyl succinic anhydride emulsion sizing agent and its preparation method |
| CN105712387A (en) * | 2016-03-15 | 2016-06-29 | 北京世纪地和控股有限公司 | Method for preparing aluminum hydroxide sulfate |
| CN115075051A (en) * | 2021-03-12 | 2022-09-20 | 荒川化学工业株式会社 | Rosin sizing agent for papermaking and paper |
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| CN115821630A (en) | 2023-03-21 |
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