CN1291922C - Nanometer titanium dioxide colloid microparticle flow aiding filter aid and preparing method thereof - Google Patents

Abstract

The present invention discloses a preparation method of a retention and filter assisting agent of colloid particles of nanometer titanium dioxide, which comprises the following steps: (1), a titanium oxygen coordination compound is prepared; (2) nanometer titanium dioxide sol is obtained by a reaction; (3), colloid is added into ammonia water for flocculation, and supernatant liquid is separated and removed in a high speed centrifugation method. Obtained gel is dissolved and dispersed in pure water, and thus, nanometer titanium dioxide colloid is obtained. Titanium dioxide colloidal particles which are prepared by using the present invention have certain crystallinity and photocatalytic activity, the consumption of the titanium dioxide colloidal particles is only 1/5 to 1/10 that a traditional retention and filter assisting agent when used as a particle retention and filter assisting agent for making paper and the titanium dioxide colloidal particles have better effects. At the same time, the attachment and the retention of the nanometer titanium dioxide colloid particles on surfaces of paper products can endow the surfaces of the paper products anti-yellowing and antibiotic capacities, and can improve optical performance and hand feelings.

Description

Nano titanium oxide colloidal particle retention filtration adjuvant and preparation method thereof

Technical field

The present invention relates to the paper making additive production technical field, specifically be meant a kind of nano titanium oxide colloidal particle retention filtration adjuvant that is applied to field of papermaking.This nano titanium oxide colloid has retention and drainage effect efficiently, can be used for removing or weakens in the mthod of white water from paper making DCS to the harm of paper machine and paper product quality, increases white water loop.

The invention still further relates to the preparation method of this nano titanium oxide colloidal particle retention filtration adjuvant.

Background technology

Carry out the whitewater closure circulation in the paper technology and be solving paper plant's water and pollute and water-saving effective way, realize the greatest difficulty of white water loop is how to eliminate or weaken the harm of DCS in the paste system.DCS derives from paper pulp solubility wood extractive (crude substance and fine-fibereds such as small molecules lignin, carbohydrate, resin) on the one hand; Derive from the auxiliary agent that adds in the tackiness agent of sneaking in the secondary stock and the paper-making process on the other hand.DCS is constantly enrichment along with the sealing reuse of plain boiled water, adsorb on surface at filler and fiber, change their Surface Physical Chemistry character, perhaps produce agglomeration between the colloid, and then influence paper machine steady running (as: increase drainage time, form gum deposits) and reduce the paper product quality that (as: dried wet tenacity reduces, the optical property variation, fracture and said minuscule hole appear in paper).Remove the method for DCS, the one, with dissolved air flotation, ultrafiltration or enzymatic treatment; The 2nd, adopt high efficiency flocculation retention aid at wet end, when fiber becomes paper, DCS is taken away with page.If obviously the latter has positive effect, it not only can make full use of starting material, and reduces DCS enrichment and outside sewage disposal load.

Though the PEO of current use (polyoxyethylene)/subsidiary double base retention filtration adjuvant has certain effect of removing to DCS in the circulation plain boiled water,, there are different many shortcomings.At first, its solubleness in water is lower, high molecular PEO anti-shear ability a little less than, be subject to the influence of factors such as temperature, water quality, thereby can cause macromolecular chain fracture, reduce the retention effect of this system; The effect that what is more important PEO must just can do very well under the synergy of subsidiary, in numerous subsidiaries, have only the polymkeric substance of phenolic hydroxy group structure the most effective, all there is toxicity in the phenolic hydroxyl structure that forms in residual monomer and the degradation process in this in process of production polymkeric substance to biological and plant, has increased ambient pollution burden.

Nano-TiO ₂Crystal particle diameter is little, specific surface is big and surface energy is high, and is positively charged less than 6.25 o'clock surfaces at PH, therefore has remarkable advantages as papermaking flocculation retention aid.Nano titanium oxide is as described below as the principle of paper retention and filter aid.DCS in the plain boiled water has negative charge, if its electric charge is neutralized, will take place to flocculate and adsorb on fiber.Nano-TiO ₂Colloid showed as positive polarity at PH less than 6.25 o'clock, and (when average particle size was 6nm, the interfacial area of unit volume was 500m owing to its big specific surface area ²/ cm ³) and the monodispersity of colloidal particle, make it have high electric density, it has good flocculation retention effect to having electronegative DCS from flocculation in theory.Its positive surface charge and high surface energy are the direct driving force of flocculation retention, and contingent process has charge neutralization, hydrogen bond action (synthetic nano-TiO in the aqueous solution ₂Have a large amount of surperficial OH) and the formation of bridged linkage.And for the fat particle in the pulp-water, nano-TiO ₂Micelle will improve wetting ability in the absorption on its surface, also help keeping and drainage.

To several microns, the DCS corpuscle is in its surface adsorption in hundreds of nanometers for traditional organic polymer retention aid particle diameter, water-soluble reduction, and the easier DCS that makes produces deposition, and paper machine and paper product are worked the mischief.And the nano colloidal tio 2 is in DCS material particle surface adsorption or agglomeration mutually, and its wetting ability is increased, and helps DCS flocculation and drainage.

Studies show that nano titanium oxide colloidal consumption only is 1/5～1/10 of conventional retention filtration adjuvant consumption, its retention and drainage effect is more superior.The nano titanium oxide colloidal particle can be given its anti-yellowing and antibacterial ability attached the staying on paper product surface simultaneously, and improve optical property and feel.

Summary of the invention

The objective of the invention is to shortcoming, a kind of nano-TiO is provided at the prior art existence ₂The colloidal particle retention filtration adjuvant, the colloidal stability that the present invention obtains is good, little and the narrow diameter distribution of particle diameter, the colloidal tio 2 particle for preparing has certain degree of crystallinity and photocatalytic activity, the nano titanium oxide colloidal particle can be given its anti-yellowing and antibacterial ability attached the staying on paper product surface simultaneously, and improve optical property and feel.

Another object of the present invention is to provide this nano-TiO ₂The preparation method of colloidal particle retention filtration adjuvant.Preparation method's temperature of reaction of the present invention is suitable, and equipment is not had special requirement, reaches water-saving purpose in to paper machine operation and the harm of paper product quality removing or weaken in the paper-making process plain boiled water DCS.

For achieving the above object, the present invention has taked following technical scheme:

A kind of preparation of nano titanium oxide colloidal particle paper retention and filter aid mainly comprises being prepared as follows step and processing condition:

The first step: the preparation of titanyl title complex

With the compound of titanium and acetic anhydride by 1: 2 to 1: 4 (mol: mixed mol), as solvent, 0～150 ℃ of reaction, the reaction times is 0.5～10 hour with non-polar solvent; Resultant obtains the mixture powder of titanyl title complex through separation, washing, drying;

Second step: take by weighing the mixture powder for preparing in the first step in reactor, add water, add acid, add stable and dispersion agent again; Each material that adds is mixed in reactor, and 25～150 ℃ of reaction 0.5～48h obtain transparent nano titanic oxide sol;

Wherein, mixture powder accounts for 0.5～15.15% of all reactive material total masses, and water accounts for 75.76～99.5%, and acid accounts for 0～7.576%, and stable and dispersion agent accounts for 0～1.5%;

Described acid is concentrated nitric acid, concentrated hydrochloric acid, phosphoric acid or sulfuric acid;

Described stable and dispersion agent is polyoxyethylene glycol or Volpo S 10;

The 3rd step: add strong aqua in the transparent nano titanic oxide sol of the second step gained colloid is flocculated, high speed centrifugation separates removes supernatant liquid, and the gel that obtains is dissolved dispersion in pure water.

The compound of described titanium comprises titanium isopropylate, four titanium butoxide, ethanolato-titanium, titanium tetrachloride acid barium and titanous chloride; Described titanyl title complex comprises acetate oxygen titanium [TiO (OOCCH ₃) ₂], alkoxy acetic acid oxygen titanium [Ti ₂O (OR) ₂(OOCCH ₃) ₄, R=C ₂H ₅, C ₃H ₇, C ₄H ₉], acetate chlorination oxygen titanium [TiOCl (OOCCH ₃)]; Described non-polar solvent comprises hexanaphthene, tetracol phenixin, benzene and sherwood oil; Described acid comprises the concentrated hydrochloric acid of 65% concentrated nitric acid or 36% or 30% sulphur nitric acid or phosphoric acid; Described stablizing with dispersion agent comprises PEG (polyoxyethylene glycol) and PVA (polyvinyl alcohol).

Nano titanium oxide colloid of the present invention is used as paper retention and filter aid, and it is 0.001～0.1% of paper pulp oven-dry weight that its titanium dioxide contains the thing consumption admittedly.PH value scope 3～6.25.

Nano titanium oxide colloid of the present invention is as paper retention and filter aid, can be that unit system also can form the double element system use with subsidiary, subsidiary comprises macromolecular compounds such as polyvinyl alcohol (PVA), polyoxyethylene glycol (PEG), carboxymethyl cellulose, carboxyethyl cellulose, Vinyl Acetate Copolymer, anionic starch.

Nano titanium oxide colloid of the present invention be used to make have anti-yellowing, antibiotic and speciality paper that opacifying property is good, its consumption is 0.001～10% of a paper pulp.

Compared with the prior art, the present invention has following beneficial effect:

The prepared titanium dioxide crystal colloidal particle particle diameter of the present invention is little, and (its gel powder is the Detitanium-ore-type crystal with certain degree of crystallinity, and has photocatalytic activity and ultraviolet absorption ability preferably for 5nm～16nm), narrow diameter distribution.In the presence of PH＜6.0 and certain ionogen, has positive zeta current potential and high electric density.When using as paper retention and filter aid, the little efficient height of consumption, its consumption only is 1/5～1/10 of a conventional reagent, and retention and drainage effect is better than conventional retention filtration adjuvant.In addition, the nano titanium oxide colloidal particle can be given its anti-yellowing and antibacterial ability attached the staying on paper product surface, and improve optical property and feel.

Description of drawings

The nano-TiO that Fig. 1 makes for embodiment 1 ₂The comparison synoptic diagram that the newsprinting paper pulping person of staying is influenced with CPAM.

Embodiment

The present invention is further illustrated below in conjunction with specific embodiment.

(1) the nano titanium oxide colloidal prepares embodiment 1～7

Preparation method's step and order as technical scheme be partly as described in (one), among the preparation embodiment 1～13 of titanyl title complex and the hydrolysis embodiment 1～7 of titanyl title complex the amount of reagent of using and preparation manipulation condition all be summarised in table 1 and the table 2.

The preparation of table 1 titanyl title complex

Embodiment	Titanium isopropylate/mol	Four titanium butoxide/mol	Titanium tetrachloride acid barium/mol	Titanous chloride/mol	Acetic anhydride/mol	Temperature of reaction/℃	Reaction times/h	Productive rate/%
									1 2 3 4 5 6 7 8 9 10 11 12 13	1 1 1 1	1 1 1	1 1 1	1 1 1	2 3 4 4 4 3 2 2 3 4 2 3 4	100 100 30 100 120 150 100 0 25 25 30 35 30	8 8 8 10 10 8 5 0.5 0.5 1 1 1 1	10 70 80 95 90 96 20 80 90 95 60 70 87

The hydrolysis of table 2 titanyl title complex

Embodiment	Titanium oxygen compound/g	Water/mL	Concentrated nitric acid/mL	Concentrated hydrochloric acid/mL	Sulfuric acid (30%)/mL	PVA/g	PEG/g	Temperature of reaction/℃	Reaction times/h	Strong aqua/mL	Particle diameter/nm
												1 2 3 4 5 6 7	10 10 20 20 40 1 100	500 1000 1000 1000 1000 200 1000	5 10 50	5 100	10 2	2 20 8	2 10 1	60 25 150 100 50 80 150	48 48 36 0.5 38 10 24	0 10 5 35 20 50 42	10 8 15 6 12 9 14

(2) the nano titanium oxide colloid is as the Application Example 1～8 of paper machine wet end retention filtration adjuvant

Preparation method's step and order as technical scheme be partly as described in (two), among the embodiment 1～8 the amount of reagent of using and preparation manipulation condition all be summarised in the table 3, wherein the nano titanium oxide colloid be in the table 1 example 6 again in table 2 example 6 make.

Table 3 nano titanium oxide colloid is as the application example of paper retention and filter aid

	TiO 2/ paper pulp oven-dry weight %	PH value	The relative turbidity of plain boiled water *	Yellowing resistance	Germ resistance	Opacifying property
							1 2 3 4 5 6 7 8	0.001 0.003 0.005 0.01 0.05 0.1 0.005 0.005	5 5 5 5 5 5 6 3	0.4 0.2 0.3 0.3 0.6 0.8 0.2 0.4	- - √ √ √ √ √ √	- - √ √ √ √ √ √	- - √ √ √ √ √ √

" √ " expression is functional."-" expression performance is general." * " dynamic drainage instrument measured value.

Contrast experiment: with the embodiment 1 prepared nano-TiO of table 2 ₂The comparison that the newsprinting paper pulping person of staying is influenced with CPAM:

CPAM is applied in the pulp and paper industry widely as a kind of retention system commonly used, and accompanying drawing 1 is itself and nano-TiO ₂As the comparison of retention aid, as shown in Figure 1, be under 5 the situation, to work as nano-TiO in the pH value ₂Consumption (ton paper oven dry stock consumption) can make relative turbidity reach 0.493 reaching 0.006%; In the pH value is 5, nano-TiO ₂At consumption 0.005～0.006%, can make relative turbidity reach 0.34～0.38, be 6 o'clock at PH, nano-TiO ₂Consumption is 0.003～0.004% o'clock, and turbidity reaches minimum, about 0.2～0.25 relatively.And CPAM reaches under 0.03% the situation relatively turbidity and reaches and only reach 0.455 at its consumption, and this illustrates nano-TiO ₂Under the situation of CPAM, will reach identical retention effect at consumption, nano-TiO is described ₂Has certain feasibility as newsprinting paper system retention aid.Some studies confirm that cationic micropartical (organic and inorganic) can obtain good retention effect with some with medium or low electric charge high molecular weight polymers application together.

Claims (2)

1, a kind of preparation of nano titanium oxide colloidal particle retention filtration adjuvant is characterized in that comprising the steps:

The first step: the preparation of titanyl title complex

The compound of titanium is mixed with acetic anhydride 1: 2 in molar ratio～4, and as solvent, 0～150 ℃ of reaction, the reaction times is 0.5～10 hour with non-polar solvent; Resultant obtains the mixture powder of titanyl title complex through separation, washing, drying;

The compound of described titanium is titanium isopropylate, four titanium butoxide, ethanolato-titanium, titanium tetrachloride acid barium or titanous chloride;

Described non-polar solvent comprises hexanaphthene, tetracol phenixin, benzene or sherwood oil;

Second step: take by weighing the mixture powder for preparing in the first step in reactor, add water, add acid, add stable and dispersion agent again; Each material that adds is mixed in reactor, and 25～150 ℃ of reaction 0.5～48h obtain transparent nano titanic oxide sol;

Wherein, mixture powder accounts for 0.5～15.15% of all reactant gross weights, and water accounts for 75.76～99.5%, and acid accounts for 0～7.576%, and stable and dispersion agent accounts for 0～1.5%;

Described acid is concentrated nitric acid, concentrated hydrochloric acid, phosphoric acid or sulfuric acid;

Described stable and dispersion agent is polyoxyethylene glycol or Volpo S 10;

The 3rd step: add strong aqua in the transparent nano titanic oxide sol of the second step gained colloid is flocculated, high speed centrifugation separates removes supernatant liquid, and the gel that obtains is dissolved dispersion in pure water.

2, the nano titanium oxide colloidal particle retention filtration adjuvant of the described method preparation of claim 1.

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