CN112934171A - Attapulgite clay surface modification method - Google Patents
Attapulgite clay surface modification method Download PDFInfo
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- CN112934171A CN112934171A CN202110144317.2A CN202110144317A CN112934171A CN 112934171 A CN112934171 A CN 112934171A CN 202110144317 A CN202110144317 A CN 202110144317A CN 112934171 A CN112934171 A CN 112934171A
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- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
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- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/17—Organic material containing also inorganic materials, e.g. inert material coated with an ion-exchange resin
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
Abstract
The invention discloses an attapulgite clay surface modification method, which comprises the following steps: performing high-temperature calcination modification, acid modification, and performing organic modification on the surface of attapulgite clay by using quaternary ammonium salt as a cationic surfactant; and (3) performing inorganic modification on the surface of the attapulgite clay by using rare earth salts (yttrium nitrate, cerium nitrate, neodymium nitrate, lanthanum nitrate, praseodymium nitrate and lanthanum chloride). According to the attapulgite clay surface modification method, the attapulgite clay is subjected to inorganic modification and inorganic-organic modification combined mode, so that the advantages of organic modification and inorganic modification are fully exerted, the specific surface area and the activated adsorption center of the attapulgite clay are increased, the adsorption capacity of the attapulgite clay is improved, and the dephosphorization effect of the modified attapulgite clay in the field of water treatment is further improved. The invention has the advantages of easily obtained raw materials, low cost, simple process and equipment requirements, easily controlled process and higher popularization and application value.
Description
Technical Field
The invention relates to the technical field of environmental protection treatment, in particular to a surface modification method for attapulgite clay.
Background
As the dissolved phosphorus (P) in the fresh water is too much, about 30-50% of water sources around the world face the eutrophication problem. The main reasons of water eutrophication are the accumulation of excessive phosphorus (P), the input of external phosphorus load and the release of endogenous phosphorus in sediments in lake water, and the regulation of total phosphorus concentration is a recognized treatment method. The adsorption method has been widely studied as a method for efficiently removing phosphorus from a water body.
Attapulgite (ATP) is a naturally available hydrous crystalline magnesium aluminum silicate mineral. ATP has a regular structure and a large specific surface area, has specific characteristics in the aspects of dispersion, high temperature resistance, salt resistance and alkali resistance, and has high adsorbability. The attapulgite reserves in China are abundant. The main deposit is located at Xuyi county, Jiangsu province. Xuyi is that the existing high-quality attapulgite 6700 ten thousand tons, and roughly estimated accounts for more than 60% of the national reserves. Natural materials such as zeolite, bentonite, montmorillonite, etc. have the problem of excellent adsorption performance but higher cost, and attapulgite is widely considered as a low-cost alternative adsorbent due to its low cost and natural abundance, unique structure and nontoxicity.
Compared with calcium, aluminum or iron, the rare earth modified adsorbent has more outstanding advantages in the process of removing phosphate, such as stronger phosphorus fixing capacity, wide pH operation range, high removal rate under low phosphate concentration and the like. At present, a phosphorus adsorbent shows a prospect for controlling phosphate in eutrophic water, namely a lanthanum modified material. Many lanthanum-based materials (e.g., lanthanum-modified bentonite (pholock), lanthanum-modified alumina, lanthanum hydroxide-modified zeolite) have been developed to reduce the phosphorus concentration in eutrophic water bodies. Lanthanum modified bentonite (PhoLock) was first developed by the Australian Federal scientific and industrial research organization and was effective in immobilizing P. The bentonite has been extensively studied and successfully applied to bodies of water in europe, the united states and australia. The PhoLock has the problems of high price and relatively low phosphorus adsorption quantity in China, and limits the popularization and application of the PhoLock in eutrophic water bodies in China. However, other reported lanthanum-modified phosphorus removal adsorbents are only limited to the indoor experimental stage and are not put into use in the domestic market. In the rare earth modified material reported at present, most of the rare earth is lanthanum, other rare earth is not reported, the abundance of the rare earth lanthanum in the earth crust is far less than that of the rare earth cerium and neodymium, and the abundance of the rare earth yttrium is equivalent to that of the rare earth yttrium, so that the rare earth modified material has good substitution. And the materials used for rare earth modification are mostly zeolite, bentonite, montmorillonite and the like, and the cost is higher. At present, no rare earth modified clay adsorbent capable of effectively treating eutrophication water body for a long time appears in domestic markets, and development of relevant treatment work of eutrophication water bodies in China is greatly hindered.
Disclosure of Invention
The invention aims to provide an attapulgite clay surface modification method and application of the modified attapulgite clay so as to solve the problems in the prior art.
An attapulgite clay surface modification method comprises the following steps:
carrying out organic modification on the surface of attapulgite clay by taking quaternary ammonium salt as a cationic surfactant;
and (3) performing inorganic modification on the surface of the attapulgite clay by adopting rare earth salt.
In the above technical scheme, the order of the steps of the organic modification and the inorganic modification of the attapulgite clay is not limited. In one embodiment, only attapulgite clay is subjected to inorganic modification; in another example, the attapulgite clay may be subjected to inorganic modification, and then the inorganic modified attapulgite clay may be further subjected to organic modification.
Further, the organic modification comprises the following specific steps: reacting a mixed reaction system containing attapulgite clay, quaternary ammonium salt and a solvent at 40-80 ℃ for 2-8 h to prepare the organic modified attapulgite clay.
Further, the mixed reaction system is subjected to reaction under the condition of constant temperature oscillation.
Further, the solvent is deionized water.
Further, the inorganic modification method comprises the following steps:
the method comprises the following steps: immersing attapulgite clay in inorganic acid for acidification to obtain acid-modified attapulgite clay;
step two: dissolving rare earth salt in deionized water; obtaining a rare earth salt solution;
step three: and adding the acidified attapulgite clay into a rare earth salt solution for reaction to obtain the rare earth modified attapulgite clay dephosphorizing agent.
Further, the inorganic acid is diluted hydrochloric acid.
Further, in the first step, the modification temperature is 20-35 ℃, and the modification time is 1-6 h.
Further, in the second step, the reaction temperature is 20-40 ℃, and the reaction time is 5-15 min.
Further, in the second step, the addition ratio of the rare earth salt to the acidified attapulgite clay is (5-10): 1.
further, in the third step, the modification temperature is 40-80 ℃, and the modification time is 2-6 hours.
In the technical scheme, the rare earth has good biocompatibility, the rare earth is used as an environment-friendly rare earth element and has strong binding force to phosphate radical, and the rare earth and phosphorus can be chemically precipitated, so that a rapid and efficient phosphorus removal effect can be achieved. The rare earth is loaded on the attapulgite, so that the dephosphorization efficiency of the attapulgite is effectively improved. The material has strong selective absorption to phosphate, especially to low-concentration phosphate.
Further, the quaternary ammonium salt is selected from one or a combination of more of cetyl trimethyl ammonium bromide, octadecyl trimethyl ammonium chloride and octadecyl trimethyl ammonium bromide, and is preferably cetyl trimethyl ammonium bromide.
Further, in the process of organically modifying the surface of the attapulgite clay, the adding amount ratio of the modified attapulgite clay to the quaternary ammonium salt is 1: (4-8).
Further, before the organic modification or the inorganic modification, the method also comprises the following steps of carrying out heat treatment on the attapulgite clay: baking the attapulgite clay for 1-3 h at the temperature of 350-650 ℃.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the attapulgite clay surface modification method, the attapulgite clay is subjected to inorganic modification and inorganic-organic modification combined mode, so that the advantages of organic modification and inorganic modification are fully exerted, the specific surface area and the activated adsorption center of the attapulgite clay are increased, the adsorption capacity of the attapulgite clay is improved, and the dephosphorization effect of the modified attapulgite clay in the water treatment field is further improved;
2. the adsorption capacity of the attapulgite clay can be improved by organically modifying the attapulgite clay and exchanging inorganic cations among layers with quaternary ammonium cations, and the enhancement of the adsorption performance of the obtained organic clay is caused by the increase of hydrophobic surface performance and interlayer spacing of expanded clay;
3. the attapulgite clay has better cation exchange capacity and good binding capacity with rare earth, so the rare earth modified attapulgite clay is an ideal phosphorus removal material. The rare earth is loaded on the attapulgite clay, so that the dephosphorization efficiency of the attapulgite clay is effectively improved, and the rare earth modified attapulgite clay is an ideal dephosphorization material;
4. the rare earth is not only abundant on the earth, but also has high cost benefit; the rare earth has high affinity to the phosphate, the phosphate combined with the rare earth does not have the release problem under the reducing condition because the valence state is not changed, and the rare earth and the phosphate have strong affinity, so that phosphorus can be effectively adsorbed in the sediment and can stably exist in the sediment, and the influence on aquatic organisms is very little; the invention has the advantages of easily obtained raw materials, low cost, simple process and equipment requirements, easily controlled process and higher popularization and application value.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a process flow of the method for inorganic modification of the surface of attapulgite clay.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1:
s1, grinding the attapulgite clay raw ore into fine powder, and sieving with a 200-mesh sieve to obtain attapulgite clay powder; baking the attapulgite clay powder at 400 ℃ for 2h to obtain modified attapulgite clay;
s2, mixing the modified attapulgite clay and hexadecyl trimethyl ammonium bromide according to the weight ratio of 5: 1, the concentration of the cetyl trimethyl ammonium bromide solution is 50mmol/L, the mixture is stirred for 6 hours at the constant temperature of 30 ℃ and the rotating speed is 400r/min, and the organic modified attapulgite clay is obtained;
s3, soaking the organically modified attapulgite clay in 0.025mol/L yttrium nitrate solution; oscillating at constant temperature of 40 ℃ for 2h at the rotating speed of 200r/min to obtain yttrium nitrate modified attapulgite clay;
and S4, drying the product obtained in the step (S3) at the temperature of 100-120 ℃, and sieving the dried product with a 200-mesh sieve. Drying to obtain yttrium nitrate modified attapulgite clay powder, wherein the drying method can be spray drying or other non-thermal processing drying methods in the prior art.
Example 2:
s1, grinding the attapulgite clay raw ore into fine powder, and sieving with a 200-mesh sieve to obtain attapulgite clay powder; baking the attapulgite clay powder at 400 ℃ for 2h to obtain modified attapulgite clay;
s2, soaking the modified attapulgite clay in a hydrochloric acid solution with the concentration of 5%, and reacting for 4h at the temperature of 20-35 ℃ to obtain acid-modified attapulgite clay;
s3, dipping the acid modified attapulgite clay into 0.03mol/L lanthanum nitrate solution, and oscillating at constant temperature of 40 ℃ for 2h at the rotating speed of 200r/min to obtain the lanthanum nitrate modified attapulgite clay;
and S4, drying the product obtained in the step (S3) at the temperature of 100-120 ℃, and sieving the dried product with a 200-mesh sieve. Drying to obtain lanthanum nitrate modified attapulgite clay powder, wherein the drying method can be spray drying or other non-thermal processing drying methods in the prior art.
Example 3:
s1, grinding the attapulgite clay raw ore into fine powder, and sieving with a 200-mesh sieve to obtain attapulgite clay powder; baking the attapulgite clay powder at 400 ℃ for 2h to obtain modified attapulgite clay;
s2, dipping the modified attapulgite clay into a hydrochloric acid solution with the concentration of 5%, and reacting for 2h at the temperature of 20-35 ℃ to obtain acid modified attapulgite clay;
s3, soaking the acid modified attapulgite clay in 0.03mol/L cerous nitrate solution, and oscillating at constant temperature of 40 ℃ for 2h at the rotating speed of 200r/min to obtain the cerous nitrate modified attapulgite clay;
and S4, drying the product obtained in the step (S3) at the temperature of 100-120 ℃, and sieving the dried product with a 200-mesh sieve. Drying to obtain cerous nitrate modified attapulgite clay powder, wherein the drying method can be spray drying or other non-thermal processing drying methods in the prior art.
Example 4:
s1, grinding the attapulgite clay raw ore into fine powder, and sieving with a 200-mesh sieve to obtain attapulgite clay powder; baking the attapulgite clay powder at 400 ℃ for 2h to obtain modified attapulgite clay;
s2, mixing the modified attapulgite clay and hexadecyl trimethyl ammonium bromide according to the weight ratio of 5: 1, the concentration of the cetyl trimethyl ammonium bromide solution is 50mmol/L, the mixture is stirred for 6 hours at the constant temperature of 40 ℃, and the rotating speed is 400r/min, so as to obtain the organic modified attapulgite clay;
s3, soaking the organically modified attapulgite clay in 0.03mol/L praseodymium nitrate solution; oscillating at constant temperature of 40 ℃ for 2h at the rotating speed of 200r/min to obtain praseodymium nitrate modified attapulgite clay;
and S4, drying the product obtained in the step (S3) at the temperature of 100-120 ℃, and sieving the dried product with a 200-mesh sieve. Drying to obtain praseodymium nitrate modified attapulgite clay powder, wherein the drying method can be a drying method in the prior art without hot processing such as spray drying.
Example 5:
s1, grinding the attapulgite clay raw ore into fine powder, and sieving with a 200-mesh sieve to obtain attapulgite clay powder; baking the attapulgite clay powder at 550 ℃ for 1h to obtain modified attapulgite clay;
s2, soaking the modified attapulgite clay in 0.03mol/L neodymium nitrate solution, and oscillating at constant temperature of 40 ℃ for 2h at the rotating speed of 200r/min to obtain the neodymium nitrate modified attapulgite clay;
and S3, drying the product obtained in the step (S2) at the temperature of 100-120 ℃, and sieving the dried product with a 200-mesh sieve. Drying to obtain neodymium nitrate modified attapulgite clay powder, wherein the drying method can be spray drying or other non-thermal processing drying methods in the prior art.
Example 6:
s1, grinding the attapulgite clay raw ore into fine powder, and sieving with a 200-mesh sieve to obtain attapulgite clay powder; baking the attapulgite clay powder at 550 ℃ for 1h to obtain modified attapulgite clay;
s2, dipping the modified attapulgite clay into 0.04mol/L lanthanum chloride solution, oscillating at constant temperature of 40 ℃ for 2h at the rotating speed of 200r/min to obtain lanthanum chloride modified attapulgite clay;
and S3, drying the product obtained in the step (S2) at the temperature of 100-120 ℃, and sieving the dried product with a 200-mesh sieve. Drying to obtain lanthanum chloride modified attapulgite clay powder, wherein the drying method can be spray drying or other non-thermal processing drying methods in the prior art.
Comparative example 1:
grinding attapulgite clay raw ore into fine powder, and sieving with a 200-mesh sieve to obtain attapulgite clay powder for application in phosphorus-containing wastewater. (Attapulgite clay is not modified at all).
Comparative example 2:
grinding attapulgite clay raw ore into fine powder, and sieving with a 200-mesh sieve to obtain attapulgite clay powder; baking the attapulgite clay powder at the temperature of 400 ℃ for 2h to obtain the modified attapulgite clay which is applied to phosphorus-containing wastewater. (Attapulgite clay is subjected to thermal modification independently).
Comparative example 3:
mixing attapulgite clay and hexadecyl trimethyl ammonium bromide according to the weight ratio of 5: 1, the concentration of the hexadecyl trimethyl ammonium bromide solution is 50mmol/L, the mixture is stirred for 6 hours at the constant temperature of 40 ℃, and the rotating speed is 200r/min, so that the organic modified attapulgite clay is obtained and is applied to the phosphorus-containing wastewater. (the attapulgite clay is organically modified independently).
Comparative example 4:
soaking the modified attapulgite clay in a hydrochloric acid solution with the concentration of 5%, and reacting for 2h at the temperature of 20-35 ℃ to obtain the acid modified attapulgite clay. Is applied to phosphorus-containing wastewater. (acid modification of attapulgite clay alone).
Comparative example 5:
grinding attapulgite clay raw ore into fine powder, and sieving with a 200-mesh sieve to obtain attapulgite clay powder; baking the attapulgite clay powder at 550 ℃ for 2h to obtain modified attapulgite clay, mixing the modified attapulgite clay with hexadecyl trimethyl ammonium bromide according to the weight ratio of 5: 1, the concentration of the hexadecyl trimethyl ammonium bromide solution is 50mmol/L, the mixture is stirred for 6 hours at the constant temperature of 40 ℃, and the rotating speed is 200r/min, so that the organic modified attapulgite clay is obtained and is applied to the phosphorus-containing wastewater. (the heat modification and the organic modification of the attapulgite clay are combined).
Comparative example 6:
grinding attapulgite clay raw ore into fine powder, and sieving with a 200-mesh sieve to obtain attapulgite clay powder; soaking the modified attapulgite clay in a hydrochloric acid solution with the concentration of 5%, and reacting for 2h at the temperature of 20-35 ℃ to obtain the acid modified attapulgite clay. Mixing the modified attapulgite clay and hexadecyl trimethyl ammonium bromide according to the weight ratio of 5: 1, the concentration of the hexadecyl trimethyl ammonium bromide solution is 50mmol/L, the mixture is stirred for 6 hours at the constant temperature of 40 ℃, and the rotating speed is 200r/min, so that the organic modified attapulgite clay is obtained and is applied to the phosphorus-containing wastewater. (a combination of modification and organic modification of attapulgite clay acid).
The removal effect of the rare earth modified attapulgite clay powder in the low-concentration phosphorus-containing wastewater is shown in Table 1
Comparative example removal effect in Low-concentration phosphorus-containing wastewater Table 2
From the above table, it can be seen that the rare earth modified attapulgite clay powder of the present invention has a good dephosphorization effect, which is better than the case of directly using attapulgite clay as a dephosphorization agent, and example 1 is the best example.
The modified attapulgite clay in comparative examples 1-6 and examples 1-6 was added to the same water samples in Table 1 to obtain the removal rate indexes in comparative examples 1-6 and examples 1-6 shown in tables 1 and 2. Through analysis, the independent organic modified attapulgite clay, the independent acid and the thermal modified attapulgite clay are respectively adopted in the comparative examples 1 to 4, and the inorganic modification and the organic modification are combined on the attapulgite clay in the comparative examples 5 and 6 by adopting the prior art, so that the obtained product is applied to the phosphorus-containing wastewater, the removal rate of the product is obviously larger than that of the products in the examples 1 to 6, namely, the effect of the product on the phosphorus-containing wastewater treatment is far inferior to that of the product in the application on the phosphorus-containing wastewater.
In conclusion, the attapulgite clay is modified by the attapulgite clay modification method, so that the modified attapulgite clay has better application effect in the field of treating eutrophic water body compared with the prior art. The attapulgite clay has low price and low applicable cost; the modifying reagent in the method does not cause pollution to the environment, and has obvious advantages in treating eutrophic water body.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned. Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. An attapulgite clay surface modification method is characterized by comprising the following steps:
carrying out organic modification on the surface of attapulgite clay by taking quaternary ammonium salt as a cationic surfactant;
and (3) performing inorganic modification on the surface of the attapulgite clay by using rare earth salts (cerium nitrate, neodymium nitrate, lanthanum nitrate, praseodymium nitrate, yttrium nitrate and lanthanum chloride).
2. The attapulgite clay surface modification method according to claim 1, wherein the inorganic modification method comprises the following steps:
the method comprises the following steps: immersing attapulgite clay in inorganic acid for acidification to obtain acid-modified attapulgite clay;
step two: dissolving rare earth salt in deionized water; obtaining a rare earth salt solution;
step three: and soaking the acidified attapulgite clay into a rare earth salt solution for reaction to obtain the rare earth modified attapulgite clay phosphorus removing agent.
3. The attapulgite clay surface modification method according to claim 2, wherein in the first step, the inorganic acid is hydrochloric acid, the concentration of the hydrochloric acid is 5-15%, the acidification temperature is 20-35 ℃, and the acidification time is 1-6 h.
4. The attapulgite clay surface modification method according to claim 2, wherein in the second step, the concentration of the rare earth salt solution is 0.02-0.2 mol/L, the reaction temperature is 20-40 ℃, and the reaction time is 5-15 min.
5. The attapulgite clay surface modification method according to claim 2, wherein in the second step, the adding amount ratio of the rare earth salt solution to the acidified attapulgite clay is (4-10): 1.
6. the attapulgite clay surface modification method according to claim 2, wherein in the third step, the modification temperature is 40-80 ℃ and the modification time is 2-6 h.
7. The attapulgite clay surface modification method according to claim 1, wherein the quaternary ammonium salt is selected from one of cetyl trimethyl ammonium bromide, stearyl trimethyl ammonium chloride and stearyl trimethyl ammonium bromide, preferably cetyl trimethyl ammonium bromide.
8. The attapulgite clay surface modification method according to claim 1, wherein in the process of organically modifying the attapulgite clay surface, the concentration of the quaternary ammonium salt is 50-100 mmol/L, and the addition amount ratio of the quaternary ammonium salt to the modified attapulgite clay is (5-8): 1.
9. the method for modifying the surface of attapulgite clay according to claim 1, wherein the method further comprises a physical modification before the organic modification or the inorganic modification: baking the attapulgite clay for 1-3 h at the temperature of 350-650 ℃.
10. The attapulgite clay prepared by the method of any one of claims 1 to 9 is applied to water quality treatment.
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