JP2021030224A - Adsorption sponge made of plant cellulose, and preparation method and application thereof - Google Patents

Abstract

To provide a method for producing an adsorption sponge made of a plant cellulose, capable of obtaining a final reaction product by one step reaction, and capable of reducing economic cost and labor cost, and to provide an adsorption sponge made of a plant cellulose.SOLUTION: After grinding or crushing a plant cellulose raw material, it is reacted with an alkaline solution and carbon disulfide, and after completion of the reaction, a solid product is collected and washed with deionized water until the solid product is to be neutral, and subjecting the washed solid product to refrigeration and freeze-dry lyophilization to obtain an adsorption sponge made of a plant cellulose. The adsorption sponge made of the plant cellulose of the present invention has a controllable shape and size, has excellent mechanical properties, is less likely to break, has an abundant pore structure that communicates with each other, has a strong adsorption capacity, and is used for removing contaminants such as heavy metal ions in waste water.SELECTED DRAWING: Figure 1

Description

The present invention belongs to the technical field of adsorbent and water treatment, and relates to an adsorbent sponge made of plant cellulose, a method for producing the same, and its application.

While advances in industrial technology have brought convenience to human life, they have caused unavoidable environmental pollution problems, especially heavy metal pollution. Since heavy metals are non-biodegradable and bioaccumulative, they can enter the human body through water, food chain, respiration, etc., accumulate in the body, and further cause serious harm to human health. Due to the rapid development of high technology such as heavy industry, electronics and aviation in China, social activities such as mining, metal smelting, chemical industry production, fossil fuel burning, mass use of pesticides and chemical fertilizers and illegal disposal of household waste are being promoted. Increasingly, heavy metals are invading the ecological environment, especially the aquatic environment. The adsorption method is the most effective treatment method for heavy metal pollution of water because it has advantages such as high efficiency, low cost, easy operation, and easy post-treatment.

Adsorbents are the core of adsorption technology, and the important issue facing us today is to produce adsorbents that are economical, efficient, and easy to separate and recover, and adsorb to meet the needs of practical applications. To achieve breakthroughs in the design and manufacture of materials. The biomass adsorbent has excellent performance as compared with the conventional adsorbent. For example, grass is a renewable resource that is inexpensive, readily available, contains abundant organic functional groups, can be effectively combined with heavy metal ions, and is susceptible to chemical denaturation. The cut grass is a waste, and when it is used as a raw material for an adsorbent, the waste can be reused and heavy metal ions in the water can be removed, which has good social and economic significance.

Currently, the denaturation treatment of grass-based biomass materials mainly includes _{treatment methods such as saponification treatment, ZnCl 2} treatment, phosphoric acid denaturation and thermal decomposition into biochar. The grass-based modified adsorbent obtained by the above modification method is almost in the form of powder, and all have a predetermined removing effect on heavy metal ions such as lead, copper and cadmium. It is difficult to realize solid-liquid separation, the difficulty of subsequent treatment is increased, and when continuous flow type wastewater treatment is performed using a device such as a fixed bed or a filling column, the powdery material causes pressure loss and adsorbent loss. It is easy to cause and increases the cost of the processing process.

Chinese Patent Application Publication No. 105489679

Patent Document 1 discloses a method for producing a nano-MgO-immobilized adsorbent, performs surface pretreatment on a wire net, then puts it in an alkaline solution containing Mg ions, and water is subjected to an in-situ reaction at a constant temperature. By obtaining a composite in which magnesium oxide is tightly wrapped in the wire mesh and controlling the heat treatment, a composite adsorbent in which nanomagnesium oxide is immobilized on the wire mesh is formed. The method for producing a nano-MgO-immobilized adsorbent according to the present invention has a simple process, and the produced adsorbent can be directly used for sewage treatment, has a high treatment effect, is easy to recover the adsorbent, and subsequently treats sewage. Reduce the process.

In order to eliminate the above-mentioned defects and deficiencies of the prior art, it is an object of the present invention to provide an adsorption sponge made of plant cellulose, a method for producing the same, and an application thereof.

The technical plan used by the present invention in order to realize the above object is as follows.
In the first aspect, the present invention
(1) A step of crushing or crushing a plant cellulose raw material to obtain a plant cellulose powder, and
(2) The plant cellulose powder treated in step (1) is weighed, an alkaline solution and carbon disulfide are added and reacted with stirring, and after the reaction is completed, the solid product is collected and washed with deionized water. Steps to do and
(3) The solid products treated in step (2) are mixed and placed in a container having a predetermined shape, then frozen until completely solidified, and then subjected to freezing vacuum drying to obtain the plant cellulose adsorption sponge. Provided is a method for producing an adsorption sponge made of plant cellulose, which comprises a step of obtaining. In the production method, a plant cellulose adsorption sponge whose shape and size can be controlled can be produced by putting the mixed solid product in a container having a required shape and size in step (3), and freeze-drying. The treatment ensures the formation of a porous structure in which the adsorption sponges made of plant cellulose communicate with each other, but the drying means such as drying cannot realize the formation of the porous structure. As shown in FIG. 1, one kind of plant cellulose adsorption sponge produced by the above-mentioned production method has excellent mechanical properties, is hard to break, can maintain a good shape even when artificially separated, and is separated. No debris is generated in the process, it is hard to break even when it hits water, no chemical sludge is generated, it has abundant pore structure that communicates with each other, it has strong water absorption capacity, and high-speed movement of adsorbents such as heavy metal ions. Accelerates the contact between heavy metal ions and the active adsorption site, shortens the adsorption time, and strengthens the adsorption effect.

In a preferred embodiment of the production method of the present invention, in the step (2), the alkaline solution is a sodium hydroxide solution, and the ratio of the plant cellulose powder, the sodium hydroxide solution and the carbon disulfide is the plant cellulose. Powder: Sodium hydroxide solution: Carbon disulfide = 0.5 to 2 g: 40 to 100 mL: 0.5 to 3 mL, and the concentration of the sodium hydroxide solution is 5% to 30%. As a more preferred embodiment of the method, in step (2), the ratio of plant cellulose powder, sodium hydroxide solution and carbon disulfide is: plant cellulose powder: sodium hydroxide solution: carbon disulfide = 1 g: 50 mL: It is 3 mL and the concentration of the sodium hydroxide solution is 14%. Applicants have tested and found that the ratio of plant cellulose powder, sodium hydroxide solution and carbon disulfide is plant cellulose powder: sodium hydroxide solution: carbon disulfide = 0.5-2 g: 40-100 mL: 0.5- When it is 3 mL and the concentration of the sodium hydroxide solution is 5% to 30%, an adsorption sponge made of plant cellulose having abundant pore structure can be smoothly produced, and in particular, plant cellulose powder, sodium hydroxide solution and two. When the ratio of carbon sulfide is plant cellulose powder: sodium hydroxide solution: carbon disulfide = 1 g: 50 mL: 3 mL and the concentration of sodium hydroxide solution is 14%, the produced plant cellulose adsorption sponge has an appearance. We found that the morphology and morphology were more beautiful, the pore structure was richer, the mechanical properties were better, and the ability to remove heavy metal ions in water was stronger.

As a preferred embodiment of the production method of the present invention, the reaction time is 6 to 24 hours in the step (2), and as a more preferred embodiment of the production method of the present invention, the step (2) In 2), the reaction time is 6 hours. Applicants have tested that when the reaction time is 6 to 24 hours, an adsorbent sponge made of plant cellulose having a regular shape can be produced, and the effective molding of the material is compared with further extending the reaction time. And low time cost can be ensured, especially when the reaction time is 6h, the produced plant cellulose adsorption sponge has a high yield, abundant pores and a high density, and a more regular and uniform internal structure. I found that it had higher elasticity.

In a preferred embodiment of the production method of the present invention, in step (2), the reaction is carried out at room temperature.

In a preferred embodiment of the production method of the present invention, in step (2), the solid product is washed with deionized water until neutral.

In a preferred embodiment of the production method of the present invention, in step (2), after completion of the reaction, the solid product is collected by a centrifugal method, and the centrifugal rotation speed is 4000 to 8000 rpm.

As a preferred embodiment of the production method of the present invention, in the step (3), the solid product is frozen in an environment of −20 ° C. or lower until it is completely solidified, and a more preferred embodiment of the production method of the present invention. In the form, in step (3), the solid product is frozen in an environment of −20 ° C. to −80 ° C. until it is completely solidified.

In a preferred embodiment of the production method of the present invention, in the step (1), the plant cellulose raw material is grass or tea leaves. The applicant has discovered that a plant cellulose raw material such as turfgrass, straw, and tea leaves, which contains a large amount of plant cellulose, can be produced in an adsorption sponge by the above production method.

As a more preferred embodiment of the production method of the present invention, in the step (1), the plant cellulose raw material is a cut turf grass.

In the second aspect, the present invention provides an adsorption sponge made of plant cellulose produced by the above production method.

In a third aspect, the present invention provides an application of the above plant cellulose adsorption sponge in wastewater treatment. The above-mentioned adsorption sponge made of vegetable cellulose can be used for adsorbing contaminants such as heavy metal ions in wastewater as a suitable filler for a water treatment device such as a fixed floor or a filling column.

The present invention has the following advantages and beneficial effects as compared with the prior art.
(1) The method for producing a plant cellulose adsorption sponge of the present invention can produce a plant cellulose adsorption sponge whose shape and size can be controlled according to actual needs.

(2) The plant cellulose adsorption sponge produced by the method for producing a plant cellulose adsorption sponge of the present invention has excellent mechanical properties, is not easily crushed even when exposed to water, and does not generate chemical sludge.

(3) The plant cellulose adsorption sponge produced by the method for producing the plant cellulose adsorption sponge of the present invention has an abundant pore structure that communicates with each other, has a strong adsorption capacity, and has a high speed of an adsorbent such as heavy metal ion. It contributes to movement, accelerates the contact between heavy metal ions and the active adsorption site, shortens the adsorption time, enhances the adsorption effect, and can remove heavy metal ions in water better than other biomass adsorbents of the prior art. ..

(4) The plant cellulose adsorption sponge produced by the method for producing a plant cellulose adsorption sponge of the present invention is easier to realize solid-liquid separation and has higher operability than the conventional powdery modified plant cellulose material. It is applied to actual water treatment work and realizes that no sludge is generated in the waste water treatment process.

(5) Compared with the conventional biomass modification treatment technique, the method for producing an adsorption sponge made of plant cellulose of the present invention does not require pre-alkalization, and the final reaction product can be obtained by a one-step reaction. , Significantly reduce the manufacturing process of materials, save time, reduce economic cost and labor cost.

It is a photograph of the plant cellulose adsorption sponge produced by the production method of the present invention, A is a complete photograph of the plant cellulose adsorption sponge, and B is a photograph after the plant cellulose adsorption sponge is separated. It is a photograph.

In order to better explain the object, technical plan and advantages of the present invention, the present invention will be further described below in combination with modes for carrying out the invention.

(Example 1)
An example of the method for producing an adsorption sponge made of plant cellulose of the present invention is
(1) The steps of washing the collected turf grass with water to remove impurities, then drying and crushing to obtain grass powder,
(2) 1 g of the grass powder treated in step (1) was weighed, 50 mL of a sodium hydroxide solution having a mass fraction of 14% and 3 mL of carbon disulfide were added, and the mixture was reacted at room temperature with continuous stirring for 6 hours. After completion of the reaction, the solid product after the reaction is centrifuged at a rotation speed of 8000 rpm, and the solid product is repeatedly washed with deionized water until it becomes neutral.
(3) The neutral solid product treated in step (2) is mixed and placed in a container of a predetermined shape, for example, a beaker having different specifications such as 50 mL and 100 mL, and then placed at −20 ° C., −50 ° C., After quick freezing at −80 ° C. or −198 ° C. until it was completely solidified, it was subjected to freezing vacuum drying to obtain a turfgrass adsorption sponge, that is, the plant cellulose adsorption sponge.

(Example 2)
An example of the method for producing an adsorption sponge made of plant cellulose of the present invention is
(1) The steps of washing the collected turf grass with water to remove impurities, then drying and crushing to obtain grass powder,
(2) 0.5 g of the grass powder treated in step (1) was weighed, 40 mL of a sodium hydroxide solution having a mass fraction of 5% and 0.5 mL of carbon disulfide were added, and the mixture was continuously stirred at room temperature for 6 hours. After the reaction is completed, the solid product after the reaction is centrifuged at 4000 rpm, and the solid product is repeatedly washed with deionized water until it becomes neutral.
(3) The neutral solid product treated in step (2) is mixed and placed in a container of a predetermined shape, for example, a beaker having different specifications such as 50 mL and 100 mL, and then placed at −20 ° C., −50 ° C., After quick freezing at −80 ° C. or −198 ° C. until it was completely solidified, it was subjected to freezing vacuum drying to obtain a turfgrass adsorption sponge, that is, the plant cellulose adsorption sponge.

(Example 3)
An example of the method for producing an adsorption sponge made of plant cellulose of the present invention is
(1) The steps of washing the collected turf grass with water to remove impurities, then drying and crushing to obtain grass powder,
(2) 0.5 g of the grass powder treated in step (1) was weighed, 70 mL of a sodium hydroxide solution having a mass fraction of 15% and 2 mL of carbon disulfide were added, and the reaction was carried out at room temperature with continuous stirring for 12 hours. After the reaction is completed, the solid product after the reaction is centrifuged at a rotation speed of 6000 rpm, and the solid product is repeatedly washed with deionized water until it becomes neutral.
(3) The neutral solid product treated in step (2) is mixed and placed in a container of a predetermined shape, for example, a beaker having different specifications such as 50 mL and 100 mL, and then placed at −20 ° C., −50 ° C., After quick freezing at −80 ° C. or −198 ° C. until it was completely solidified, it was subjected to freezing vacuum drying to obtain a turfgrass adsorption sponge, that is, the plant cellulose adsorption sponge.

(Example 4)
An example of the method for producing an adsorption sponge made of plant cellulose of the present invention is
(1) The steps of washing the collected turf grass with water to remove impurities, then drying and crushing to obtain grass powder,
(2) 0.5 g of the grass powder treated in step (1) is weighed, 100 mL of a sodium hydroxide solution having a mass fraction of 30% and 3 mL of carbon disulfide are added, and the reaction is carried out at room temperature with continuous stirring for 24 hours. After the reaction is completed, the solid product after the reaction is centrifuged at 4000 rpm, and the solid product is repeatedly washed with deionized water until it becomes neutral.
(3) The neutral solid product treated in step (2) is mixed and placed in a container of a predetermined shape, for example, a beaker having different specifications such as 50 mL and 100 mL, and then placed at −20 ° C., −50 ° C., After quick freezing at −80 ° C. or −198 ° C. until it was completely solidified, it was subjected to freezing vacuum drying to obtain a turfgrass adsorption sponge, that is, the plant cellulose adsorption sponge.

(Example 5)
An example of the method for producing an adsorption sponge made of plant cellulose of the present invention is
(1) The steps of washing the collected turf grass with water to remove impurities, then drying and crushing to obtain grass powder,
(2) Weigh 2 g of the grass powder treated in step (1), add 40 mL of sodium hydroxide solution having a mass fraction of 5% and 0.5 mL of carbon disulfide, and react with continuous stirring at room temperature for 6 hours. After the reaction is completed, the solid product after the reaction is centrifuged at a rotation speed of 8000 rpm, and the solid product is repeatedly washed with deionized water until it becomes neutral.
(3) The neutral solid product treated in step (2) is mixed and placed in a container of a predetermined shape, for example, a beaker having different specifications such as 50 mL and 100 mL, and then placed at −20 ° C., −50 ° C., After quick freezing at −80 ° C. or −198 ° C. until it was completely solidified, it was subjected to freezing vacuum drying to obtain a turfgrass adsorption sponge, that is, the plant cellulose adsorption sponge.

(Example 6)
An example of the method for producing an adsorption sponge made of plant cellulose of the present invention is
(1) The steps of washing the collected turf grass with water to remove impurities, then drying and crushing to obtain grass powder,
(2) Weigh 2 g of the grass powder treated in step (1), add 80 mL of sodium hydroxide solution having a mass fraction of 20% and 1.5 mL of carbon disulfide, and react with continuous stirring at room temperature for 15 hours. After the reaction is completed, the solid product after the reaction is centrifuged at a rotation speed of 8000 rpm, and the solid product is repeatedly washed with deionized water until it becomes neutral.
(3) The neutral solid product treated in step (2) is mixed and placed in a container of a predetermined shape, for example, a beaker having different specifications such as 50 mL and 100 mL, and then placed at −20 ° C., −50 ° C., After quick freezing at −80 ° C. or −198 ° C. until it was completely solidified, it was subjected to freezing vacuum drying to obtain a turfgrass adsorption sponge, that is, the plant cellulose adsorption sponge.

(Example 7)
An example of the method for producing an adsorption sponge made of plant cellulose of the present invention is
(1) The steps of washing the collected turf grass with water to remove impurities, then drying and crushing to obtain grass powder,
(2) 2 g of the grass powder treated in step (1) was weighed, 100 mL of a sodium hydroxide solution having a mass fraction of 30% and 3 mL of carbon disulfide were added, and the mixture was reacted at room temperature with continuous stirring for 24 hours. After completion of the reaction, the solid product after the reaction is centrifuged at a rotation speed of 8000 rpm, and the solid product is repeatedly washed with deionized water until it becomes neutral.
(3) The neutral solid product treated in step (2) is mixed and placed in a container of a predetermined shape, for example, a beaker having different specifications such as 50 mL and 100 mL, and then placed at −20 ° C., −50 ° C., After quick freezing at −80 ° C. or −198 ° C. until it was completely solidified, it was subjected to freezing vacuum drying to obtain a turfgrass adsorption sponge, that is, the plant cellulose adsorption sponge.

It should be noted that the above examples are merely for explaining the technical plan of the present invention, do not limit the scope of claims of the present invention, and describe the present invention in detail with reference to suitable examples. As described above, a person skilled in the art can make amendments to the technical plan of the present invention, or make the same substitution without departing from the substance and scope of the technical plan of the present invention.

Claims (10)

(1) A step of crushing or crushing plant cellulose to obtain plant cellulose powder, and
(2) The plant cellulose powder treated in step (1) is weighed, an alkaline solution and carbon disulfide are added and reacted with stirring, and after the reaction is completed, the solid product is collected and washed with deionized water. Steps to do and
(3) The solid products treated in step (2) are mixed and placed in a container having a predetermined shape, then frozen until completely solidified, and then subjected to freezing vacuum drying to obtain the plant cellulose adsorption sponge. A method for producing an adsorption sponge made of plant cellulose, which comprises a step of obtaining. In the step (2), the alkaline solution is a sodium hydroxide solution, and the ratio of the plant cellulose powder, the sodium hydroxide solution and the carbon disulfide is such that the plant cellulose powder: sodium hydroxide solution: carbon disulfide = 0.5. The production method according to claim 1, wherein the amount is ~ 2 g: 40 to 100 mL: 0.5 to 3 mL, and the mass concentration of the sodium hydroxide solution is 5% to 30%. In the step (2), the ratio of the plant cellulose powder, the sodium hydroxide solution and the carbon disulfide is plant cellulose powder: sodium hydroxide solution: carbon disulfide = 1 g: 50 mL: 3 mL, and the mass of the sodium hydroxide solution. The production method according to claim 2, wherein the concentration is 14%. The production method according to claim 1, wherein in the step (2), the reaction time is 6 to 24 hours. The production method according to claim 1, wherein in the step (2), the reaction is carried out at room temperature. The production method according to claim 1, wherein in the step (2), the solid product is washed with deionized water until it becomes neutral. The production method according to claim 1, wherein in the step (3), the solid product is frozen in an environment of −20 ° C. or lower until it is completely solidified. The production method according to claim 1, wherein the plant cellulose raw material is grass or tea leaves. An adsorption sponge made of plant cellulose produced by the production method according to any one of claims 1 to 8. Application of the plant cellulose adsorption sponge according to claim 9 in wastewater treatment.