CN109610217A - The composition of organic pollutant deposition is controlled in pulping and paper-making production - Google Patents
The composition of organic pollutant deposition is controlled in pulping and paper-making production Download PDFInfo
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- CN109610217A CN109610217A CN201910039414.8A CN201910039414A CN109610217A CN 109610217 A CN109610217 A CN 109610217A CN 201910039414 A CN201910039414 A CN 201910039414A CN 109610217 A CN109610217 A CN 109610217A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
- D21C5/02—Working-up waste paper
- D21C5/022—Chemicals therefor
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
- D21C5/02—Working-up waste paper
- D21C5/025—De-inking
- D21C5/027—Chemicals therefor
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/008—Prevention of corrosion or formation of deposits on pulp-treating equipment
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/08—Removal of fats, resins, pitch or waxes; Chemical or physical purification, i.e. refining, of crude cellulose by removing non-cellulosic contaminants, optionally combined with bleaching
- D21C9/086—Removal of fats, resins, pitch or waxes; Chemical or physical purification, i.e. refining, of crude cellulose by removing non-cellulosic contaminants, optionally combined with bleaching with organic compounds or compositions comprising organic compounds
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/64—Paper recycling
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Abstract
The invention discloses the composition for controlling organic pollutant deposition in a kind of production of pulping and paper-making, the effective component of the composition includes: biological enzyme i) with peroxide hydrolysis function；Ii) hydrogen peroxide and/or the predecessor of hydrogen peroxide can be generated；In the composition i) and ii) weight part ratio be 1: 0.1-200.Composition of the present invention can significantly control stickies problem in pulping and paper-making production, the especially deposition of stickum, sicker is reduced to the possible negative effect of papermaking and harm, improve the efficiency and product quality of paper production, reduce energy consumption, production cost has been saved for papermaking enterprise, has improved economic profit, and applied widely.
Description
It is October 19, entitled " slurrying in 2016 that the application, which is application No. is the 2016109123190, applying date,
In paper production control organic pollutant deposition composition and papermaking process " divisional application.
Technical field
The invention belongs to pulp and paper technology field, in particular to control organic pollutant is heavy in a kind of pulping and paper-making production
Long-pending composition.
Background technique
In paper production industry, the field of a growing interest is the recycling and secondary use of waste paper；However, from waste paper
Or removing impurity from the process-stream for handling waste paper is the key that can recycle waste paper.In the paper making process, organic
The deposition (being called precipitating) of pollutant is all very unfavorable to paper product quality and paper production efficiency, this problem most important two
A concrete reason is pitch deposition and Stickies deposit.Wherein, the main component of resin deposit is naturally present in timber
And released in slurrying and paper-making process；For physics angle, " resin deposit " in slurry usually by bonding
The microcosmic particle of agent material (natural or artificial) is formed and is accumulated on papermaking paper or pulping equipment.And " sicker precipitating "
Particle usually in the slurry of regenerated fiber, general chemical structure are characterized in the glue (adhesives) of synthesis
With the adhesives such as hot melt adhesive (hot melts), including but not limited to: heat fusing object, pressure-sensitive adhesive (PSA), latex and viscous
Mixture.
In the past, the depositional phenomenon of resin and sicker has respectively typical embodiment in not homologous ray, this is because
Papermaking at that time almost only uses protofibre or only uses regenerated fiber.In order to control these problems independent of one another, it will usually
There are completely different processing chemicals and countermeasure.But trend in recent years is in all systems all gradually using again
Raw fiber, therefore " Stickies deposit " can also occur while generation " pitch deposition ", cause sicker to sink jointly with resin
Long-pending organic pollutant deposition problem.
These deposits are easy in pulp storage tank wall, papermaking cabinet, u-shaped case, paper machine wires, wet press felts, drying cylinder
It is found in felt, drying chamber and calendar stacks.Organic pollutant deposition can not only remain on the metal surface of system, can also
It retains on plastics and synthetic surface, deleterious effect is caused to paper production.Such as in machine, woollen blanket, u-shaped case case and stream
It starches on box part, is unfavorable for slurrying or papermaking, or even influence running efficiency, reduces production capacity etc..If organic pollutant is heavy
On process equipment in paper manufacturing systems, the organic pollutant being deposited on consistency regulator and other detection instruments will cause product
These components can not normal use, cause system operatio difficult.In addition, organic deposition will cause paper hole, dirt and its
Its paper defects, these defects can be such that the quality of paper declines, and be not used to subsequent handling, such as coating, printing and dyeing power day work or printing.
Although can carry out downtime to paper machine, we are not intended to that this downtime occurs, because this
It will cause the corresponding loss of productivity, and when these deposits fracture and are mixed into paper, the presence of these pollutants is again
A meeting more step causes the deterioration of paper quality.It include dispersion, screening for removing/controlling sicker/pollutant mechanical means
And cleaning.Impurity is ground into smaller and smaller particle with dispersion, until they are invisible in final product.Make us losing
Regret, when product winding, even if the presence of " invisible " impurity fails to remove the mutual viscous of adjacent layer, and these impurity are still
Weaken total appearance of product with can dramatically.Sieve and centrifugal cleaner can also be used for from fiber stream remove sicker, resin and
Slag object, the size and shape difference in their holes or slit based on impurity and sieve separate fiber from impurity.However, sieve
Son cannot be removed less than sieve pore or can be deformed enough so that by the impurity of sieve pore, which has limited sieves to separate fiber from impurity
Effect.Different specific gravity based on impurity and fiber, centrifugal cleaner separate fiber from impurity.However, working as impurity and fibre
When the relative density of dimension is similar, separating effect is bad.
Viscosity describes the bond properties of impurity, by reducing the viscosity of impurity, can significantly reduce in technical process
Impurity adheres to the tendency of paper machine wire and other surfaces.The method for reducing contaminant tack in the past includes the change of process-stream
And mechanical treatment.Certain methods are concentrated on using on Repulpable or reproducible adhesive.More universal methods include
Using chemical addition agent to change impurity or make impurity vanishing viscosity.In general, the chemical addition agent includes that silicate mineral is such as sliding
Stone and bentonite, these mineral and surfactant are adhered to the surface of impurity, therefore change the surface nature of cohesive material,
To reduce viscosity.However, these methods during unsticking using mineral there are numerous disadvantages, including dosage it is big, when sudden and violent
It is exposed to loss in efficiency when shear stress, and there may be negative effect etc. to other operations and product quality.
United States Patent (USP) US3,992,249 discloses the anionic vinyl polymer using the hydrophobic group containing 25-85%
Organic deposition is controlled, wherein hydrophobic group includes styrene, methyl styrene, long-chain fat alkyl etc., anionic group
Including acrylic acid, methacrylic acid, styrene sulfonic acid etc..Nonionic polymeric detackifiers are as control resin and Stickies deposit
Substance be it is known in the art that its deposition that be used to control the resin and sicker in slurrying and paper manufacturing systems.For example,
It is proposed with vinyl alcohol-acetate ethylene copolymer can control slurrying to United States Patent (USP) US 4,871,424 and US 4,886,575 respectively
With the resin and Stickies deposit in paper manufacturing systems.In routine techniques, being often used DeTac, (U.S. Hercules Inc. is produced
Product) control organic deposition, but it is the problem is that effect difference and narrow application range, especially for fatty acid soaps
Pitch deposition is substantially to no effect.
The non-ionic associative type polymer for using hydrophobically modified is introduced in 0568229 A1 of European patent EP, such as hydrophobic is changed
The carboxyethyl cellulose ether (HMHEC) of property, can prevent organic pollutant in slurrying and paper manufacturing systems from depositing from paper pulp.The U.S. is special
Sharp US 5,723,021 and US 7,166,192 disclose non-ionic polyalcohol vinyl alcohol-acetate ethylene copolymer and
The combination of HMHEC and cation type polymer.Recently, United States Patent (USP) US 8,048,268 discloses with the thickening of hydrophobically modified amino
Agent (hydrophobically modified ethoxylated aminoplast thickener) control organic deposition is asked
Topic.But these methods really fully effective cannot solve the problems, such as organic deposition, have the defects that ineffective.
In addition, oneself knows the pollutant catabolic gene agent that enzyme can be effective as in slurrying and paper manufacturing systems.Its principle is: fat
Enzyme and esterase are protein catalysts, they can promote the glycerol ester hydrolysis in resin Composition, can also be anti-with sicker
It answers, so that its viscosity reduces, eliminates and/or inhibit deposition.As United States Patent (USP) US 5,176,796 is elaborated with containing mechanical paper
During slurry manufacture paper, using lipase by the main component of resin, i.e., nonpolar triglycerides is hydrolyzed to water-soluble sweet
Oil and polarity fatty acid.United States Patent (USP) US 5,507,952, US 5,356,800,6,471,826 B2, US patent publications of US
It reports in 20061 No. 0048908 and 02/095127 A2 of International patent publications WO and is contained using lipolytic enzyme to hydrolyze
The polymer of vinyl acetate, to reduce the viscosity of pollutant, the pollutant polyvinyl alcohol is the gluing in typical recycled writing paper
Object pollutant component.
But it not is the best approach for controlling organic pollutant in slurrying and papermaking application that enzyme, which is used alone,.For example, many
A well known problem is exactly that can be given birth to the metal ion reaction in water using the fatty acid that lipase decomposes resin and generates
At slightly solubility fat soap, cause to deposit, and when resin content is higher, or even pitch deposition of the ratio without lipase treatment
It is more serious.Fusing point after saponification of fats is higher than the fusing point of unconverted preceding resin, and viscosity is bigger, insoluble in general organic molten
Agent, thus it is more difficult to control.For this purpose, elaborating one kind in United States Patent (USP) US 5,256,252 and US 5,667,634 in slurrying and making
The method of pitch deposition is controlled during paper comprising lipase and cation type polymer is applied in combination, to reduce cellulose
Fatty acid concentration in slurry water phase.Similar method is disclosed in 6,471,826 B2 of United States Patent (USP) US, this method combination makes
The organic pollutant in recycled writing paper is controlled at least one esterase and cation type polymer.U.S. Patent Application Publication
A kind of method for reducing or preventing accumulation of pollutants is disclosed in 2004/0194903 Al, this method is including the use of one kind
Or the liquid felt conditioner of a variety of enzymes and non-enzymatic, the conditioner is by one or more surfactants and/or one kind or more
Kind anionic or cationic dispersing agent or polymer are constituted.
A kind of improve to the adhesive in paper-making process is disclosed in 2006/0048908 A1 of U.S. Patent Application Publication
The method of removal or control with adhesive contaminant comprising be applied in combination one or more enzymes and one or more absorbents or
Adsorbent.The absorbent or adsorbent are selected from natural or synthetic inorganic and organic granular comprising cation, the yin of crosslinking
Ion or nonionic organic micro particles.
But existing cellulase treatment organic pollutant and the less viscous technology of drop have due to the selectivity of biological enzyme
Effect property is confined to a certain or certain a kind of cohesive material.And the type of the stickum in paper making pulp is more, composition variation
Greatly, therefore, current biological enzyme is undesirable to the effect of stickies control.
In short, up to the present, there are no a kind of really fully effective methods for solving organic deposition problems.And papermaking
Industry is thirsted for obtaining a kind of cost-effective technology to solve the problems, such as this puzzlement paper production many years of organic deposition very much.
Summary of the invention
Based on this, the present invention provides the composition that organic pollutant deposition is controlled in a kind of production of pulping and paper-making.
The specific technical solution for solving above-mentioned technical problem is as follows:
The composition of organic pollutant deposition is controlled in a kind of production of pulping and paper-making, the effective component of the composition includes
Following components:
I) with the biological enzyme of peroxide hydrolysis function, the biological enzyme is Perhydrolase (perhydrolases)；
Ii) hydrogen peroxide and/or predecessor (the hydrogen peroxide of hydrogen peroxide can be generated
precursors)；
In the composition i) and ii) weight part ratio be 1: 0.1-200.
In wherein some embodiments, i) described in Perhydrolase be one or more Perhydrolases, the Perhydrolase
It include: the carboxylic ester hydrolases for acting on ester bond, thioester hydrolase, orthophosphoric ester monohydrolase or phosphodiester hydrolase, effect
In ehter bond thioether hydrolase and act on the polypeptide hydrolase of peptide bond.
In wherein some embodiments, the polypeptide hydrolase is alpha-amido-acyl-peptide hydrolase, peptidyl-amino sour water
Solve at least one of enzyme, acyl-amino acid hydrolase, dipeptides base hydrolase or peptidyl-peptide hydrolase.
In wherein some embodiments, i) described in Perhydrolase be acetates hydrolase and peptidyl-peptide hydrolase.
In wherein some embodiments, ii) described in can to generate the predecessor of hydrogen peroxide be that can pass through chemical reaction
Or zymetology reaction generates the compound of hydrogen peroxide；The zymetology reaction is can be by oxidase catalyzed oxidation zymolyte and oxygen
Gas or air generate the reaction of hydrogen peroxide.
In wherein some embodiments, the oxidizing ferment be glucose oxidase, monoamine oxidase, xanthan acid oxidase,
Urate oxidase, oxalate oxidase, half lactate oxidase, cellulose oxidation enzyme, polyphenol oxidase, fatty alcohol oxidase or fat
At least one of aldehyde oxidase.
In wherein some embodiments, the oxidizing ferment is in glucose oxidase, monoamine oxidase or phenol oxidase
It is at least one.
In wherein some embodiments, in the composition i) and ii) weight part ratio be 1: 0.1-30.
In wherein some embodiments, in the composition i) and ii) weight part ratio be 1: 0.1-20.
In wherein some embodiments, in the composition i) and ii) weight part ratio be 1: 0.1-10.
In wherein some embodiments, in the composition i) and ii) weight part ratio be 1: 0.1-5.
In wherein some embodiments, in the composition i) and ii) weight part ratio be 1: 0.5-5.
In wherein some embodiments, in the composition i) and ii) weight part ratio be 1: 1-2.
Another object of the present invention is to provide it is a kind of with above-mentioned composition control organic pollutant deposition papermaking process,
Include the following steps:
(1) aqueous cellulosic papermaking slurry material A is formed；
(2) above-mentioned composition is added in cellulosic papermaking slurry material A described in step (1) and is reacted, obtain pulping
Expect B；
(3) paper making pulp B described in step (2) is served into net, drainage, solid component forms page；
(4) page for obtaining step (3) obtains paper product by squeezing and drying.
In wherein some embodiments, the additive amount of composition described in step (2) is dry finish 0.01-20kg per ton.
In wherein some embodiments, the additive amount of composition described in step (2) is dry finish 0.10-11kg per ton.
In wherein some embodiments, the additive amount of composition described in step (2) is dry finish 0.4-5.5kg per ton.
The temperature of step (2) described reaction is 10-80 DEG C in wherein some embodiments, and time 5-600min, pH are
3-10。
In wherein some embodiments, the temperature of step (2) described reaction is 20-80 DEG C, time 20-300min.
In wherein some embodiments, the temperature of step (2) described reaction is 45-65 DEG C, time 50-150min.
Another object of the present invention is to provide above-mentioned compositions to control organic pollutant deposition in pulping and paper-making production
In application.
The composition and papermaking process tool of organic pollutant deposition are controlled in a kind of pulping and paper-making production of the present invention
Have the advantage that and the utility model has the advantages that
Many experiments of the present invention through inventor obtain peroxide hydrolase and hydrogen peroxide and/or energy by special ratios
The composition for enough generating the predecessor composition of hydrogen peroxide can significantly control organic pollutant deposition in pulping and paper-making production, special
It is not the deposition of stickum, and has been determined that the optimum proportioning of each component and the composition are raw in pulping and paper-making in the composition
Optimum addition in production handles paper pulp raw material using the composition, since it can be with the organic pollutant in paper pulp (especially
Stickum, including ink) oxydrolysis reaction occurs, to change the physicochemical property of organic pollutant in paper pulp, reduce
The viscosity of organic pollutant, so that this substance is easier to be separated and removed in pulping process, thus prevent, reduce, removing,
Organic pollutant (especially stickum) deposition problems in paper pulp papermaking system even are eliminated, reduce organic pollutant to papermaking
Possible negative effect and harm improve the efficiency and product quality of paper production, are especially reduction of disconnected paper rate, and
Energy consumption is reduced, production cost has been saved for papermaking enterprise, has improved economic profit；In addition, composition of the present invention also has
Advantage applied widely.
Detailed description of the invention
Fig. 1 is that reaction principle of the composition of the present invention in pulping and paper-making production in control organic pollutant deposition is shown
It is intended to；
Fig. 2 is the surface deposition results that blank group ONP/OMG produces newsprint organic pollutant (sicker) in embodiment 1
Figure；
Fig. 3 is the surface deposition results figure of control group 1 (left figure) and control group 2 (right figure) sicker in embodiment 1；
Fig. 4 is the surface deposition results figure of 2 sicker of experimental group in embodiment 1；
Fig. 5 is the surface deposition results figure of 3 sicker of experimental group in embodiment 1；
Fig. 6 is the surface deposition results figure of 8 sicker of experimental group in embodiment 1；
Fig. 7 is the form result figure in embodiment 2 before test with the Stickies deposit on dryer scraper surface after experiment；Its
In, A is before testing, and B is after testing；
Fig. 8 is the comparing result figure in embodiment 2 before test with Stickies deposit amount after test.
Specific embodiment
In the present invention, term " Perhydrolase " or " peroxide hydrolase " (English: perhydrolases) refer to, can urge
The peroxide hydrolase substrate for changing its selection is hydrolyzed, while with hydroperoxidation, can result in the mistake second of sufficient amount
The biological enzyme of sour or other organic peracids；Perhydrolase of the invention generates the very high ratio crossed and hydrolyzed with hydrolysis, these
Enzyme crosses the ratio hydrolyzed with hydrolysis because its is higher, and is particularly well suited for being used in very wide use condition and on the way.The present invention
Perhydrolase be characterized as being with unique primary sequence, tertiary structure or quaternary structure, specifically describe public
In the document opened, such as Chinese invention patent application CN103333870A, United States Patent (USP) US7960151, United States Patent (USP) 7927854,
United States Patent (USP) 7384787, United States Patent (USP) 7754460 have enumeration.
Other than the Perhydrolase of document above description, the peroxide hydrolase that a variety of hydrolases can be used in the present invention,
It include but is not limited to the carboxylic ester hydrolases (EC 3.1.1.6) for acting on ester bond, thioester hydrolase (EC 3.1.2), mono phosphoric acid ester
Ester hydrolase (EC 3.1.3) and phosphodiester hydrolase (EC 3.1.4)；Act on the thioether hydrolase (EC of ehter bond
3.3.1)；Act on alpha-amido-acyl-peptide hydrolase (EC 3.4.x), the peptidyl-aminoacidase (EC of peptide bond
3.4.11), acyl-amino acid hydrolase (EC 3.4.21), dipeptides base hydrolase and peptidyl-peptide hydrolase (EC 3.4.x)；Institute
There are these enzymes to have high hydrolysis and hydrolysis ratio excessively.Among them, preferably acetates hydrolase and peptidyl-hydrolase polypeptide
Enzyme.Suitable hydrolase includes: that (1) belongs to the protease of peptidyl-peptide hydrolase class (for example, pepsin, pepsin B, solidifying
Galactenzyme (rennin), trypsase, chymotrypsin A, chymotrypsin B, elastoser, enterokinase, histone
It is enzyme C, papain, chymopapain, ficin (ficin), fibrin ferment, fibrinolysin, feritin, withered
Straw mycoproteinase, by mould PEPA A, clostridiopetidase A, fusiform brood cell glycosides bacterium PEPB B, kallikrein, pepsin, tissue egg
White enzyme D, bromelain (bromelin), keratinase, chymotrypsin C, pepsin C, by mould skin enzyme B, urine swash
Enzyme, Carboxypeptidase A and B and aminopeptidase)；(2) carboxylic ester hydrolases includes Carboxylesterase, lipase, pectinesterase and chlorophyllase；
(3) have and exceed hydrolysis to the enzyme of hydrolysis ratio.Particularly effective among them is lipase, and shows high water excessively
Solution is to the esterase of hydrolysis ratio, and carries out esterase, cutinase and the lipase of protein engineering transformation.
Term " heterozygosis Perhydrolase (hybrid perhydrolases) " and " fusion Perhydrolase (fusion
Perhydrolases) " refer to, from least two different albumen or the engineered obtained protein of " parental generation " albumen.?
In preferred embodiment, these parental proteins are homologous each other.For example, in some embodiments it is preferred that heterozygosis cross hydrolysis
Enzyme or fusion protein contain a kind of N-terminal of albumen and the C-terminal of the albumen homology object.In some preferred embodiments, this
Two ends are merged into the clean property protein corresponding to overall length.
Term " cross hydrolyze " or " crossing hydrolysis " (English: perhydrolysis) refer to hydrogen peroxide with it is certain specific
Chemical substance carry out oxidation reaction and generate peroxidating substance, for example, ethyl acetate and hydrogen peroxide cross hydrolysis can
To express as follows:
Term " peracid (peracid) " refers to the organic acid RCOO with following chemical structure2H, in formula R be aliphatic chain or
Fragrant chain, such as peracetic acid (peracetic acid) are crossed oleic acid (per oleic acid).
Term " peroxide hydrolase substrate " refers to, all fatty races and aromatic series carboxylic in paper making raw material and production technology
Under the catalysis of peroxide hydrolase hydrolysis and peroxide occur for acid/alcohol ester type compound and hydrogen peroxide, the substrate
Change reaction, generates peracid or peroxy acid；Obtaining the key component of this reaction effect (hydrolysis is crossed by enzymatic and generates peracid)
It is enzyme, zymolyte and hydrogen peroxide.In some preferred embodiments, zymolyte is selected from following one or more esters material
Material: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, octanoic acid, king's acid, class acid, 12 a heatable brick bed acid, 14 a heatable brick bed acid, 16 a heatable brick bed acid, ten
Eight a heatable brick bed acid and oleic acid；The hydrogen peroxide can directly be added in batches, or constantly " in situ to generate "；Described is " in situ to produce
It is raw " refer to, the hydrogen peroxide (H being added in production technology2O2) predecessor, form be robotics decompose generate peroxide
Change the percarbonate of hydrogen or crosses canopy hydrochlorate；Or hydrogen peroxide is generated by the oxidizing ferment of biological enzyme, the oxidizing ferment
Example includes glucose oxidase, generates hydrogen peroxide by catalysis glucose and oxygen reaction,
(1)
(2)
Term " oxidizing ferment " refers to have and aoxidize by using oxygen as electron acceptor catalysis oxidation zymolyte and oxygen
Gas reduction becomes the biological enzyme of hydrogen peroxide, including but not limited to following biological enzyme type: glucose oxidase (glucose
Oxidase EC 1.1.3.4), monoamine oxidase (monoamine oxidase), xanthan acid oxidase (xanthine
Oxidase), urate oxidase (urate oxidase), oxalate oxidase (oxalate oxidase), half lactate oxidase
(galactose oxidase), cellulose oxidation enzyme (polysaccharide monooxygenase), polyphenol oxidase
(polyphenol oxidase), fatty alcohol oxidase (alcohol oxidase) and fatty aldehyde oxidase (aldehyde
oxidase)。
" xanthan acid oxidase " (I.U.B.:1.1.3.22) refers to, has and is catalyzed following xanthic acid oxidation reaction
Biological enzyme, including
(i)
(ii)
Term " urate oxidase " (EC 1.7.3.3) refers to that a kind of catalysis uric acid is oxidized to the enzyme of 5- hydroxyl isouric acid:
Uric acid+O2+H2O → 5- hydroxyl isouric acid+H2O2
Term " monoamine oxidase (abbreviation MAO) " (EC 1.4.3.4) refers to there is catalysis Monoamines oxidative deamination
The enzyme of reaction；The Monoamines are that one kind contains " aromatic ring-CH2-CH2-NH2" compound.Monoamine oxidase is catalyzed
, it is that monoamine is oxidized deamination, generates the reaction of hydrogen peroxide, ammonia and corresponding aldehyde.Reaction formula can be written as:
Term " glucose oxidase " (I.U.B.:1.1.3.4) refers to there is the following oxidation of catalysis glucose and oxygen
The biological enzyme of reduction reaction:
Term " half lactate oxidase " (I.U.B.:1.1.3.9) refers to there is the following oxidation of catalysis galactolipin and oxygen
The biological enzyme of reduction reaction:
Term " polyphenol oxidase " is also known as Tyrosine (I.U.B.:1.14.18.1) and refers to, has catalysis Tyrosine and oxygen
Following redox reaction biological enzyme:
Term " fatty alcohol oxidase " (EC 1.1.3.13) is also known as alcohol oxidase enzyme and refers to, has the fat such as catalysis alcohol
The biological enzyme of the following redox reaction of pure and mild oxygen:
Term " fatty aldehyde oxidase " (EC 1.1.3.13) refers to there is the following oxidation of catalysis fatty aldehyde and oxygen also
The biological enzyme of original reaction:
Term " oxalate oxidase " (EC 1.2.3.4) refers to there is the following redox reaction of catalysis oxalic acid and oxygen
Biological enzyme:
Term " fiber oxidation enzyme (Cellulose Oxidative Enzymes) " refers to glycan oxygenase
(polysaccharide monooxygenase, PMO), " the glycan oxygenase " refer to family's molecular weight in 20-
50Kba, the small molecule metalloenzyme (metalloenzyme) for containing copper (II) can carry out oxygenation or dehydrogenation with fiber surface
Oxidation reaction, to change the biological enzyme of fiber surface chemical property.Other titles of glycan oxygenase include poly- glucose oxygenation
Enzyme claims poly- glucose monooxygenase (polysaccharide monooxygenase, PMO), cracking performance glycan oxygenase
(lytic polysaccharide monooxygenase, LPMO) and 61 race (glycosyl of glucosides hydrase
Hydrolase 61, GH61).
Term " fiber oxidation enzymatic compositions " refers to that the composition contains the following two kinds component, and a component is that glycan oxygen closes
Enzyme (polysaccharide monooxygenase) and another component are able to maintain or increase to fiber oxidation enzyme activity
The adminicle of property, wherein the adminicle can be one or more compounds of following compound, the reaction of (1) fiber oxidation enzyme
Substrate oxygen or the scavenger (radical of oxygen release compound (oxygen precursors), (2) reaction product
Scavengers) and (3) to fiber oxidation enzyme have facilitation protein.
Term " reaction substrate of fiber oxidation enzyme " refers to other than fiber, necessary to glycan oxidizing ferment reacts
Electron acceptor -- oxygen；The reaction substrate can be provided in such a way that oxygen, air or oxygen release compound, this
In invention oxygen release compound refer to peroxide or ozone, wherein peroxide include hydrogen peroxide, sodium peroxide,
Calper calcium peroxide, potassium peroxide.
Term " cellulolytic enzyme " refer to it is all by hydrolysis come the biological enzyme of degraded cellulose, at present usually
The terms such as cellulolytic enzyme and cellulase, fiber hydrolase and cellulase are used alternatingly.According to cellulose degraded bottom
The different modes of action can be divided into 3 classes when object:
(1) endo cellulase is also referred to as endoglucanase (Endoglucanase, EG；EC 3.2.1.4)；
(2) exocellulase is also referred to as cellobiohydrolase (Cellobiohydrolase, CBH；EC
3.2.1.91)；
(3) beta-glucosidase (β-glucosidase, BGL；EC 3.2.1.21).
(a) endo cellulase (also known as endoglucanase, endo-1,4- β-D-glucanase, EC 3.2.1.4),
The fermentoid mainly acts on the noncrystalline domain inside cellulose, and random hydrolysis β-Isosorbide-5-Nitrae-glycosidic bond cuts long chain cellulose molecule
It is short, the small molecule cellulose of a large amount of non reducing ends is generated, molecular size range is about 23-146KD；
(b) exocellulase (also known as exoglucanase, exo-1,4- β-D-glucanase, EC 3.2.1.91),
Such enzyme effect hydrolyzes β-Isosorbide-5-Nitrae-D-14 glycosidic bond, successively cuts next cellobiose molecule in cellulose linear molecule end,
Therefore also known as cellobiohydrolase (cellobiohydrolase, CBH) molecular weight about 38-118KD.
(c) cellobiase (also known as beta-glucosidase, β-Isosorbide-5-Nitrae-glucosidase, EC 3.2.1.21), abbreviation BG.
The cellodextrin of cellobiose or solubility is generally hydrolyzed into glucose molecule by this fermentoid, and molecular weight is about 76KD.
Term " enzymatic activity (CMCase) of cellulase " refers to that cellulose components are at them by cellulose degradation at Portugal
The enzymatic activity of glucan in terms of the ability of grape sugar, cellobiose and disaccharides.The activity of cellulase generally uses carboxymethyl cellulose
The reduction of the solution viscosity of element determines.
The component of peroxide hydrolase according to the present invention, which can be, is separately added into papermaking with the product of its single enzyme component
In the process, two components can also be separately added into different positions or be mixed into a product formula and be added in paper-making process
The same position, to reach optimal effect.
Purpose and effect according to the present invention using peroxide hydrolase are using peroxide hydrolase to sticky in slurry
While material direct hydrolysis is reacted, generated peracetic acid reacts the further Strong oxdiative of cohesive material, changes sticky material
The physicochemical properties of material reduce sticky (specific reaction principle to reach the content for reducing stickum in paper making pulp
Schematic diagram is referring to Fig. 1).Since peracetic acid or peroxy acid can all can be carried out strong oxidation reaction to all cohesive materials, with
Traditional carboxylic ester hydrolases is compared just for esters cohesive material, and method of the invention has broad spectrum activity, avoids carboxylate water
Solve the unicity problem of enzyme.
Unit " kg/T " of the present invention refers to kilogram number to add materials in oven dry stock per ton.
Below with reference to specific embodiment, the present invention will be further described.
Embodiment 1
The papermaking process of organic pollutant deposition is controlled in a kind of production of pulping and paper-making, this method is mainly used for useless to recycle
Control during old newspaper production newsprint to organic pollutant (i.e. following sickers).
One, material
The slurry of deinking old and useless newspaper slurry (ONP) is obtained from one, Guangdong newsprint production paper plant.Conventional sicker control
Preparation uses the registered trademark product of U.S. Ashland companyMake reference comparison.In addition to comparison
StickyAway (polyvinyl acetate hydrolase, polyvinyl acohol acetate-esterase) is by the U.S.
Outside Novozymes company provides, Perhydrolase and the biological enzyme product such as other oxidizing ferment and hydrolase are by auspicious occasion star biology skill
Art (Guangzhou) Co., Ltd provides, and subsequent number is that intra-company's enzyme encodes.Hydrogen peroxide (concentration 30%W/V) He Guoyi
Acid is provided by Guangdong Zhongcheng Chemicals Inc..
Two, specific method
Using face powder mixerSimulate pulping and paper-making production in process in paper pulp mixing and
Dry process, measurement at different conditions sicker mixed cylinder and stirring flap surface deposition, then more various groups
Divide the influence to organic deposition.
The condition of deposition test are as follows: 100 grams of dry cellulosic slurry (dry pulp weight) adds water by the aqueous of slurry adjusting to 10%
Cellulosic papermaking slurry material is reacted using different Perhydrolase compositions (as shown in table 1) with cellulosic papermaking slurry material, reaction temperature
Degree is 65 DEG C, and the reaction time is 120 minutes, and stirring intensity is medium.
Deposition test terminates, and sicker is in mixed cylinder and the deposition for stirring flap surface under measurement different condition, specifically
As shown in table 1 below.
Three, result
As a result referring to table 1, Fig. 2-Fig. 6, as can be seen from Table 1, Perhydrolase composition experimental group 1-8 used in the present embodiment
There is better effect than control group 1-3 to the effect of control Stickies deposit, especially when selecting suitable combination, table
Existing effect be it is optimal, Stickies deposit amount can be substantially reduced；Fig. 2 is the Stickies deposit of blank group as a result, Fig. 3 is control
As a result, Fig. 4 and Fig. 5 is the typical consequence of experimental group 2 and 3, Fig. 6 is for 1 (left figure) of group and the Stickies deposit of control group 2 (right figure)
The typical consequence of experimental group 8.It can be seen that Perhydrolase composition substantially reduces Stickies deposit amount from above-mentioned chart.
Perhydrolase combination compares the deposition of sicker under 1 different condition of table
Note: 1. " stirring valve surfaces " are to be glued the area of object covering divided by the ratio of stirring valve total surface area；
2. " vessel surface deposition " is to be glued the area of object covering divided by the ratio of the inner surface of container gross area；
3. " Perhydrolase 3116 " belongs to acetate esterase (EC3.1.1.6) class；
4. " Perhydrolase 3421 " belongs to protease (EC4.2.x) class.
Embodiment 2
East China heavy packages paper manufacturing enterprise produces corrugated paper and boxboard.In recent years, the sicker of OCC waste paper is recycled
It is on the rise.The said firm once tried a variety of stickies control products, did not all obtain satisfied effect.It is produced according to the paper plant
Raw material, sicker composition and process conditions, in the composite formula of the multiple Perhydrolases of laboratory test, finally select one
A optimal composition (experimental group 4 in embodiment 1, i.e., clean enzyme as described belowTM) on machine test, and be based on
The stickies control enzyme of the product (Bark Mann, U.S. product, the entitled Maxizyme of trade mark) of StickyAway is scheduled to last
Direct comparison in nearly two months.As a result as shown in table 2 and Fig. 7-8.
Table 2 the result shows that, under identical use cost, the clean enzyme based on PerhydrolaseTMThan being based on
The effect of StickyAway esterase (Maxizyme) is much better.For example, testing clean enzymeTMBefore, the disconnected paper that sicker causes
Time is extremely serious in front baking section, and increases with woollen blanket the time being used to increase and (it is preceding shown for experiment to be shown in Table the period in 2
Data)；In addition clean enzymeTMLater, disconnected paper gradually reduces, and after three weeks, the paper time of breaking is from clean enzymeTMBefore test
Have decreased within average daily 153 minutes 36 minutes (being shown in Table in 2 the period as data shown in clean enzyme).On the contrary, deactivating cleaning enzymeTM
Later, although stickies control enzyme (Maxizyme) product of addition offshore company, the disconnected paper time continues to increase, such as following table
Shown (being shown in Table the experimental data that the period in 2 is comparison).
Influence of the table 2 based on the complex enzyme formula of Perhydrolase to the paper that breaks caused by sicker
Note: comparison=product (Maxizyme) test based on StickAway；After comparison=stop StickyAway product
(Maxizyme) after, any stickies control product is not added.
Fig. 7 compared before testing and (do not add any stickies control product, scheme A) sicker and the examination on dryer scraper surface
(clean enzyme is used after testingTM, scheme B) dryer scraper surface Stickies deposit form.As it can be seen that after using Perhydrolase,
Not only the amount (Fig. 8) of Stickies deposit greatly reduces, but also viscosity and form (including color) significantly change (Fig. 7).
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (5)
1. controlling the composition of organic pollutant deposition in a kind of pulping and paper-making production, which is characterized in that the composition has
Imitating ingredient includes following components:
I) with the biological enzyme of peroxide hydrolysis function, the biological enzyme is peroxide hydrolase；
Ii) hydrogen peroxide and/or the predecessor of hydrogen peroxide can be generated；
In the composition i) and ii) weight part ratio be 1: 0.1-200.
2. controlling the composition of organic pollutant deposition, feature in a kind of pulping and paper-making production according to claim 1
Be, i) described in peroxide hydrolase be carboxylic ester hydrolases, thioester hydrolase, orthophosphoric ester monohydrolase, hydrolysis of phosphate diester
At least one of enzyme, thioether hydrolase or polypeptide hydrolase；And/or
Ii the predecessor that hydrogen peroxide can be generated described in) is that can generate hydrogen peroxide by chemical reaction or zymetology reaction
Compound；The zymetology reaction is to generate the anti-of hydrogen peroxide by oxidase catalyzed oxidation zymolyte and oxygen or air
It answers.
3. controlling the composition of organic pollutant deposition, feature in a kind of pulping and paper-making production according to claim 2
Be, the oxidizing ferment be glucose oxidase, monoamine oxidase, xanthan acid oxidase, urate oxidase, oxalate oxidase,
At least one of half lactate oxidase, cellulose oxidation enzyme, polyphenol oxidase, fatty alcohol oxidase or fatty aldehyde oxidase.
4. controlling the combination of organic pollutant deposition in a kind of pulping and paper-making production according to claim 1-3
Object, which is characterized in that in the composition i) and ii) weight part ratio be 1: 0.1-30.
5. controlling the composition of organic pollutant deposition, feature in a kind of pulping and paper-making production according to claim 4
Be, in the composition i) and ii) weight part ratio be 1: 0.1-10.
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| CN114182557B (en) * | 2021-12-13 | 2023-03-17 | 上海金堂轻纺新材料科技有限公司 | Tea saponin composition for pulping and papermaking, preparation method and application thereof |
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| CN101421383A (en) * | 2006-03-02 | 2009-04-29 | 金克克国际有限公司 | Surface active bleach and dynamic pH |
| CN101548045A (en) * | 2006-11-06 | 2009-09-30 | 赫尔克里士公司 | Pitch and stickies control in pulp and papermaking processes |
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| US20110212868A1 (en) * | 2010-03-01 | 2011-09-01 | Neil Joseph Lant | Solid Laundry Detergent Composition Having an Excellent Anti-Encrustation Profile |
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| US20080078519A1 (en) * | 2006-09-21 | 2008-04-03 | Enzymatic Deinking Technologies, Llc | Rapid Fatty Acid Assay for Use in Pulp Pitch Control |
| DK2292743T3 (en) * | 2003-12-03 | 2013-11-25 | Danisco Us Inc | Perhydrolase |
| CA2637691A1 (en) * | 2006-02-14 | 2007-08-23 | Novozymes North America, Inc. | Chemical pulp treatment compositions and methods |
| US20120036649A1 (en) * | 2008-09-10 | 2012-02-16 | Danisco Us Inc. | Enzymatic textile bleaching compositions and methods of use thereof |
| US7960528B1 (en) * | 2009-12-07 | 2011-06-14 | E. I. Du Pont De Nemours And Company | Perhydrolase providing improved peracid stability |
| CN106053301B (en) * | 2016-06-06 | 2019-01-15 | 瑞辰星生物技术（广州）有限公司 | The method for monitoring sicker distribution situation in pulp and paper production |
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| CN101421383A (en) * | 2006-03-02 | 2009-04-29 | 金克克国际有限公司 | Surface active bleach and dynamic pH |
| CN101548045A (en) * | 2006-11-06 | 2009-09-30 | 赫尔克里士公司 | Pitch and stickies control in pulp and papermaking processes |
| CN101680172A (en) * | 2007-05-16 | 2010-03-24 | 巴科曼实验室国际公司 | Methods to control organic contaminants in fibers |
| US20110212868A1 (en) * | 2010-03-01 | 2011-09-01 | Neil Joseph Lant | Solid Laundry Detergent Composition Having an Excellent Anti-Encrustation Profile |
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| WO2021057159A1 (en) * | 2019-09-25 | 2021-04-01 | 山鹰国际控股股份公司 | Processing technology for removing adhesive substances from paper pulp |
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