CN108360296B - Paper deacidification agent and preparation method and application thereof - Google Patents
Paper deacidification agent and preparation method and application thereof Download PDFInfo
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- CN108360296B CN108360296B CN201810184524.9A CN201810184524A CN108360296B CN 108360296 B CN108360296 B CN 108360296B CN 201810184524 A CN201810184524 A CN 201810184524A CN 108360296 B CN108360296 B CN 108360296B
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- deacidification agent
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/18—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00 of old paper as in books, documents, e.g. restoring
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Abstract
The invention discloses a paper deacidification agent, which comprises the following components: populus tremuloides extract, soluble tetraborate, nano metal hydroxide, metal bicarbonate and water. Also disclosed is a method for preparing the paper deacidification agent, comprising: (1) adding the extract of Populus tremuloides into water, stirring and mixing, and filtering; (2) adding nano metal hydroxide, metal bicarbonate and soluble tetraborate into the filtrate obtained in the step (1), fully stirring and carrying out ultrasonic treatment for 0.5-1.5 h; (3) standing and aging for 1-12 h to obtain the paper deacidification agent. The paper deacidification agent disclosed by the invention is environment-friendly and harmless, has no safety influence on human bodies and the environment, is thorough and uniform in deacidification, has sufficient alkali residues, long effect duration, is not easy to return acid, does not damage paper, has certain antibacterial activity, and is beneficial to long-term storage of the paper after being used.
Description
Technical Field
The invention belongs to the field of paper deacidification, relates to a paper deacidification agent and a preparation method thereof, and particularly relates to a deacidification agent for a plasma paper deacidification method.
Background
Organizations such as libraries, archives, museums, etc. store tens of thousands of paper materials such as archives, books, calligraphy and painting, newspapers, etc. These paper documents are valuable heritage of human civilization and have important historical and cultural values that cannot be copied. Over time, under the influence of various factors, a large amount of paper documents have phenomena of mildew, pulverization and fragmentation, pollution and worm damage, and the like, so that the protection of the cultural data faces a serious challenge. To preserve these acidified paper documents, a number of paper deacidification studies have been conducted. The basic principle of deacidification of paper is to neutralize acidic materials in paper with alkaline materials. Specifically, weak alkali is permeated into the paper to neutralize the generated free acid, and certain reserve alkalinity is reserved in the deacidified paper to restore certain softness, inhibit further fiber hydrolysis and acid gas corrosion in the atmosphere, and delay the paper deterioration speed.
In general, deacidification agents need to meet the following requirements: (1) the method is safe and reliable, and intermediate products, byproducts and final products generated in the deacidification chemical reaction process are nontoxic and harmless, cannot generate gas with strong pungent smell, and cannot generate chemical substances harmful to human bodies; (2) the deacidification agent is environmentally friendly in a deacidification process. Intermediates, by-products and end-products produced during the deacidification chemical reaction should be environmentally friendly and not produce environmentally hazardous materials; (3) the deacidification agent can not damage any part in the document, and the deacidification agent can not damage the material forming the document, including paper, writing materials such as ink, dye, stamp and the like. The document can not fade or bleed after deacidification. The deacidification agent does not damage paper fibers and does not generate chemical changes with fibers, fillers, dyes, pigments and the like which damage documents; (4) low production cost and easy operation.
At present, deacidification agents can be mainly divided into three types: aqueous, nonaqueous and gaseous deacidification. Aqueous solutions are excellent in safety and deacidification effect, but are prone to paper deformation.
The nonaqueous deacidification agent has uneven deacidification and poor effect, and is easy to cause paper color fading and peculiar smell. And the non-aqueous organic deacidification agent is inflammable and has high biotoxicity, which threatens the health of operators, some organic matters (Freon) are harmful to the environment, the use of the deacidification of the gaseous deacidification agent depends on expensive and complicated professional equipment, the potential safety hazard of inflammable and explosive exists, and the residual quantity of alkali is small.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a paper deacidification agent and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a paper deacidifying agent comprising: populus tremuloides extract, soluble tetraborate, nano metal hydroxide, metal bicarbonate and water.
Preferably, the paper deacidification agent comprises the following components in percentage by weight: 0.5-7 wt% of populus tremuloides extract, 0.01-3 wt% of soluble tetraborate, 0.01-2 wt% of nano metal hydroxide, 0.01-1 wt% of metal bicarbonate and the balance of water.
The populus diversifolia is a tree growing in a dry saline-alkali desert of the Xinjiang tacrolimus and can absorb a large amount of salt from soil. The Populus diversifolia contains various alkaline substances such as organic alkali, alkaline inorganic salt and the like, and can be extracted by an artificial extraction method. The natural alkaline substances extracted from the plants have better compatibility with paper fibers, so that the natural alkaline substances can more easily enter the interior of the paper fibers, so that the natural alkaline substances can be subjected to neutralization reaction with acidic substances in the paper, and a certain amount of alkaline substances remain in the paper, so that the paper can be stored for a longer time.
The preparation method of the populus diversifolia extract comprises the following steps: cleaning leaves and barks of the populus isobavayi, crushing, sieving, adding a mixed solution of water/acetone/glycerol with the weight of 8-10 times of the weight of powder, extracting for 2-3 times at 60-80 ℃, wherein the extraction time is 1-2 h each time, filtering, concentrating the filtrate to the relative density of 1.0-1.2, cooling, adding ethanol to ensure that the alcohol content is 50-70%, stirring uniformly, standing, filtering, recovering ethanol from the filtrate, aging for 24-72 h at 20-40 ℃, and filtering to obtain the populus isobavayi extract.
Preferably, the mass ratio of the leaves and the barks of the selected populus isobavayi is 1: 1 to 5. The invention selects the specific part of the populus isobavayi to extract the effective components, the leaves and barks of the populus isobavayi are rich in alkaline substances and have higher cellulose content, the alkaline substances at the part have better compatibility with paper fibers, the damage to the paper can be effectively avoided, and meanwhile, the populus isobavayi extract also has certain antibacterial activity and is beneficial to the long-term storage of the paper.
In the mixed liquid of water/acetone/glycerol, the volume ratio of water, acetone and glycerol is 1: 0.5-1.5: 0.5 to 1.5. According to the method, the water/acetone/glycerol mixed solution is adopted to extract the populus tremuloides, so that the alkaline substances in the populus tremuloides can be effectively extracted, the ethanol is added after the extraction until the ethanol content is 50-70%, the impurities such as protein and polysaccharide can be effectively removed, and the alkaline substances are extracted and retained to the greatest extent.
Preferably, the soluble tetraborate salt is at least one of sodium tetraborate, potassium tetraborate, lithium tetraborate, and calcium tetraborate.
Preferably, the nano metal hydroxide is at least one of nano magnesium hydroxide and nano calcium hydroxide.
Preferably, the metal bicarbonate is at least one of magnesium bicarbonate, calcium bicarbonate and potassium bicarbonate.
The invention also provides a preparation method of the paper deacidification agent, which comprises the following steps:
(1) adding the extract of Populus tremuloides into water, stirring and mixing, and filtering;
(2) adding nano metal hydroxide, metal bicarbonate and soluble tetraborate into the filtrate obtained in the step (1), fully stirring and carrying out ultrasonic treatment for 0.5-1.5 h;
(3) standing and aging for 1-12 h to obtain the paper deacidification agent.
Preferably, in the step (2), stirring is carried out at 50-80 ℃.
The invention also provides an application of the paper deacidification agent, and the application method of the paper deacidification agent comprises the following steps:
(1) scanning the paper to be protected by utilizing normal-pressure air low-temperature plasma;
(2) and spraying the atomized deacidification agent on the surface of the paper treated by the plasma.
Compared with the prior art, the invention has the following beneficial effects:
(1) the paper deacidification agent is environment-friendly and harmless, and has no safety influence on human bodies and the environment.
(2) The paper deacidifying agent disclosed by the invention is used for deacidifying and protecting paper, and the pH value of the paper can be controlled in a proper range after deacidification, namely the pH value is 7.1-8.5. The deacidification effect is achieved, the paper is ensured to be in a weakly alkaline environment, the preservation time of the paper is prolonged, and the damage to paper fibers caused by overhigh alkalinity is avoided.
(3) The deacidification agent of the invention is used for deacidifying paper, so that the deacidification is thorough and uniform, sufficient alkali residue is obtained, and the effect duration is long.
(4) The deacidification agent of the invention is used for deacidifying paper by plasma, has lasting deacidification effect and is not easy to return acid.
(5) The paper deacidification agent disclosed by the invention has no damage to paper, and can not cause the situations of writing halation, pigment color difference and the like.
(6) The paper deacidification agent has certain antibacterial activity, and is beneficial to long-term storage of paper after being used.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
Cleaning 3kg of iso-leaf poplar leaves and 7kg of iso-leaf poplar barks, crushing, sieving by a 10-mesh sieve, adding a mixed solution of water/acetone/glycerol (the volume ratio of the water to the acetone to the glycerol is 1: 0.7: 1) of which the weight is 10 times of that of the powder, extracting for 3 times at 70 ℃, filtering, concentrating the filtrate until the relative density is 1.10-1.15, cooling, adding ethanol until the ethanol content is 65%, stirring uniformly, standing, filtering, recovering the ethanol from the filtrate, aging for 72 hours at 30 ℃, and filtering to obtain the iso-leaf poplar extract.
Adding Populus tremuloides extract 700g into water 9209g, stirring thoroughly, mixing, and filtering; adding 30g of nano magnesium hydroxide, 60g of magnesium bicarbonate and 1g of lithium tetraborate into the filtrate, fully stirring at 80 ℃, and carrying out ultrasonic treatment for 0.5 h; standing and aging for 1h to obtain the paper deacidification agent.
Example 2
Adding 600g of the populus tremuloides extract prepared in the example 1 into 9339g of water, fully stirring and mixing, and filtering; adding 1g of nano calcium hydroxide, 30g of calcium bicarbonate and 30g of sodium tetraborate into the filtrate, fully stirring at 70 ℃, and carrying out ultrasonic treatment for 1 h; standing and aging for 2h to obtain the paper deacidification agent.
Example 3
Adding 500g of the populus tremuloides extract prepared in example 1 into 9344g of water, fully stirring and mixing, and filtering; adding 40g of nano calcium hydroxide, 55g of nano magnesium hydroxide, 1g of potassium bicarbonate and 60g of potassium tetraborate into the filtrate, fully stirring at 50 ℃, and carrying out ultrasonic treatment for 1 h; standing and aging for 4h to obtain the paper deacidification agent.
Example 4
Adding 400g of the populus tremuloides extract prepared in the example 1 into 9365g of water, fully stirring and mixing, and filtering; adding 60g of nano magnesium hydroxide, 40g of calcium bicarbonate, 15g of potassium bicarbonate, 70g of sodium tetraborate and 50g of lithium tetraborate into the filtrate, fully stirring at 65 ℃ and carrying out ultrasonic treatment for 1 h; standing and aging for 6h to obtain the paper deacidification agent.
Example 5
Adding 300g of the populus tremuloides extract prepared in the example 1 into 9335g of water, fully stirring and mixing, and filtering; adding 130g of nano calcium hydroxide, 30g of calcium bicarbonate, 35g of magnesium bicarbonate, 90g of potassium tetraborate and 90g of lithium tetraborate into the filtrate, fully stirring at 60 ℃, and carrying out ultrasonic treatment for 1 h; standing and aging for 8h to obtain the paper deacidification agent.
Example 6
Adding 200g of the Chinese populus extract prepared in the example 1 into 9285g of water, fully stirring and mixing, and filtering; adding 120g of nano magnesium hydroxide, 80g of nano calcium hydroxide, 40g of magnesium bicarbonate, 45g of potassium bicarbonate, 130g of sodium tetraborate and 100g of potassium tetraborate into the filtrate, fully stirring at 55 ℃, and carrying out ultrasonic treatment for 1 h; standing and aging for 10h to obtain the paper deacidification agent.
Example 7
Adding 50g of the populus tremuloides extract prepared in the example 1 into 9390g of water, fully stirring and mixing, and filtering; adding 160g of nano magnesium hydroxide into the filtrate, stirring for 30min, and performing ultrasonic treatment for 1 h; adding 30g of calcium bicarbonate, 30g of potassium bicarbonate, 40g of magnesium bicarbonate, 100g of sodium tetraborate, 100g of lithium tetraborate and 100g of potassium tetraborate, fully stirring at room temperature and carrying out ultrasonic treatment for 1.5 h; standing and aging for 12h to obtain the paper deacidification agent.
Comparative example 1
The paper deacidification agent used in this comparative example was a saturated aqueous solution of sodium tetraborate and was used in the same manner as in example 1.
Comparative example 2
The paper deacidification agent used in this comparative example was the same as in example 1, except that the populus tremuloides extract was replaced with potassium bicarbonate of equal mass, and the use method was the same as in example 1.
Comparative example 3
The comparative example differs from example 1 only in that the method of preparation of the populus tremuloides extract used is as follows:
cleaning 10kg of poplar isoloba inflorescence, crushing, sieving with a 10-mesh sieve, adding a mixed solution of water/acetone/glycerol (the volume ratio of water to acetone to glycerol is 1: 0.7: 1) with the weight of powder being 10 times of the weight of the powder, extracting for 3 times at 70 ℃, filtering, concentrating the filtrate until the relative density is 1.10-1.15, cooling, adding ethanol until the alcohol content is 65%, stirring uniformly, standing, filtering, recovering ethanol from the filtrate, aging for 72 hours at 30 ℃, and filtering to obtain the poplar isoloba extract.
Except for this, the kinds and amounts of the components in the paper deacidification agent, the preparation method and the use method were the same as those in example 1.
Comparative example 4
The comparative example differs from example 1 only in that the method of preparation of the populus tremuloides extract used is as follows:
cleaning 3kg of iso-leaf poplar leaves and 7kg of iso-leaf poplar barks, crushing, sieving by a 10-mesh sieve, adding water with the weight 10 times of the powder, extracting for 3 times at 70 ℃, filtering, concentrating the filtrate until the relative density is 1.10-1.15, cooling, adding ethanol until the ethanol content is 65%, stirring uniformly, standing, filtering, recovering ethanol from the filtrate, aging for 72 hours at 30 ℃, and filtering to obtain the iso-leaf poplar extract.
Except for this, the kinds and amounts of the components in the paper deacidification agent, the preparation method and the use method were the same as those in example 1.
Scanning the acidified paper by adopting normal-pressure air low-temperature plasma, and uniformly spraying the atomized paper deacidification agents prepared in the examples 1-7 and the comparative examples 1-4 on the surface of the paper. The paper after protection treatment is subjected to pH value detection according to GB/T1545-2008, tensile strength detection according to GB/T12914-2008, folding endurance detection according to GB/T457-2008 and wet-heat aging treatment according to GB/T22894-2008, and the pH value is tested, so as to quantify the protection effect and judge the influence of the protection treatment on the paper, wherein the results are shown in Table 1.
TABLE 1
The results in table 1 show that the paper deacidification agent prepared by using the populus tremuloides extract and the inorganic base at the specific position has good deacidification effect, the paper after deacidification has moderate alkalinity, and the pH value is controlled to be 7.1-8.5. Meanwhile, the deacidification treatment improves the mechanical property of paper fibers and is beneficial to long-term preservation of paper. The deacidification agent has good compatibility with paper fibers, complete deacidification effect and difficult acid return.
Claims (7)
1. The paper deacidification agent is characterized by comprising the following components in percentage by weight: 0.5-7 wt% of populus tremuloides extract, 0.01-3 wt% of soluble tetraborate, 0.01-2 wt% of nano metal hydroxide, 0.01-1 wt% of metal bicarbonate and the balance of water;
the preparation method of the populus diversifolia extract comprises the following steps: cleaning leaves and barks of the populus isobavayi, crushing, sieving, adding a mixed solution of water/acetone/glycerol with the weight of 8-10 times of the weight of powder, extracting for 2-3 times at 60-80 ℃, wherein the extraction time is 1-2 h each time, filtering, concentrating the filtrate to the relative density of 1.0-1.2, cooling, adding ethanol to ensure that the alcohol content is 50-70%, stirring uniformly, standing, filtering, recovering ethanol from the filtrate, aging for 24-72 h at 20-40 ℃, and filtering to obtain the populus isobavayi extract.
2. The paper deacidification agent according to claim 1, wherein the volume ratio of water, acetone and glycerol in the mixed solution of water/acetone/glycerol is 1: 0.5-1.5: 0.5 to 1.5.
3. The paper deacidification agent according to claim 1, wherein the soluble tetraborate salt is at least one of sodium tetraborate, potassium tetraborate, lithium tetraborate, and calcium tetraborate.
4. The paper deacidification agent according to claim 1, wherein the nano metal hydroxide is at least one of nano magnesium hydroxide and nano calcium hydroxide.
5. The paper deacidification agent according to claim 1, wherein the metal bicarbonate is at least one of magnesium bicarbonate, calcium bicarbonate and potassium bicarbonate.
6. A method for producing the paper deacidification agent according to any one of claims 1 to 5, characterized by comprising the steps of:
(1) adding the extract of Populus tremuloides into water, stirring and mixing, and filtering;
(2) adding nano metal hydroxide, metal bicarbonate and soluble tetraborate into the filtrate obtained in the step (1), fully stirring and carrying out ultrasonic treatment for 0.5-1.5 h;
(3) standing and aging for 1-12 h to obtain the paper deacidification agent.
7. The use of the paper deacidification agent according to any one of claims 1 to 5, wherein the paper deacidification agent is used by the following method:
(1) scanning the paper to be protected by utilizing normal-pressure air low-temperature plasma;
(2) and spraying the atomized deacidification agent on the surface of the paper treated by the plasma.
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| CN201810184524.9A CN108360296B (en) | 2018-03-06 | 2018-03-06 | Paper deacidification agent and preparation method and application thereof |
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| CN109371754B (en) * | 2018-09-25 | 2020-12-25 | 首都博物馆 | Paper deacidification agent composition and deacidification method for acidified paper |
| CN110552241A (en) * | 2019-07-12 | 2019-12-10 | 华南理工大学 | Method for deacidifying and enhancing acidified and aged paper documents by using sodium silicate or borax and polyamide epichlorohydrin compound |
| CN114703697B (en) * | 2022-04-28 | 2023-05-09 | 杭州众材科技股份有限公司 | Paper deacidification method adopting two-component water-based deacidification agent |
| CN114934403A (en) * | 2022-05-18 | 2022-08-23 | 杭州众材科技股份有限公司 | Paper bacteriostatic deacidification agent, preparation method and application |
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| CN102146267B (en) * | 2010-12-29 | 2012-12-19 | 刘舜强 | Paste for mounting ancient calligraphy and paintings and preparation method thereof |
| CN102242529B (en) * | 2011-04-28 | 2014-03-12 | 广东工业大学 | Pressurizing, atomizing and deacidifying device and method for pressurizing, atomizing and deacidifying by using same |
| CN102268842B (en) * | 2011-07-28 | 2013-03-13 | 广东工业大学 | Method for deacidifying paper by using soluble tetraborate as paper deacidifying agent |
| CN103276627A (en) * | 2013-05-28 | 2013-09-04 | 南京博物院 | Multifunctional nano compound treating fluid for protecting paper cultural relics and preparation method thereof |
| CN107326742A (en) * | 2017-07-23 | 2017-11-07 | 复旦大学 | A kind of depickling of paper fibre and reinforcement guard method |
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