A rapid detection and evaluation method for zeolite loading and zeolite loading uniformity in zeolite composite materials

Abstract

The present application relates to the field of product quality inspection and evaluation of composite materials, and in particular, a method for rapid inspection and evaluation of zeolite loading and zeolite loading uniformity in zeolite composite materials, specifically as follows: in a multi-component system containing zeolite, by sequentially performing selective coloring operations and enhanced color development operations on zeolite microparticles, the originally colorless zeolite microparticles are transformed into zeolite particles with a specific dark color, and the color of the non-zeolite components is not changed during the above-mentioned treatment process, thereby transforming the microscopic zeolite loading determination technical problem into a macroscopic color depth analysis problem. The inspection and evaluation method of the present application has the advantages of being fast, low-cost, and capable of parallel operation. Based on the inspection and evaluation method provided by the present application, an analysis technology for continuous and non-omission load uniformity information of the inspection area can be developed.

Description

Technical Field

[0001] The present application relates to the field of product quality detection and evaluation of composite materials, and in particular to a method for rapid detection and evaluation of zeolite loading and zeolite loading uniformity in zeolite composite materials. Background Art

[0002] A zeolite composite material is a composite material containing both a zeolite component and a non-zeolite component. The zeolite component is microscopic zeolite particles, typically less than 50 microns in diameter. The non-zeolite component is typically a macroscopic matrix material, but in some cases can also be a microscopic powder material. For the purposes of this application, the term "zeolite composite material" also includes a powdered mixed material product obtained by directly mixing zeolite powder and non-zeolite powder.

[0003] For zeolite composite materials, zeolite is an active component or an important component, and its loading amount and loading uniformity are both important evaluation indicators of product quality.

[0004] The loading of a zeolite composite material refers to the amount of zeolite present in the composite material. This loading can be calculated in different ways depending on the application. For example, it can be calculated as a percentage by dividing the mass of the zeolite by the total mass of the zeolite composite material; it can also be calculated as a percentage by dividing the mass of the zeolite by the mass of the matrix material in the zeolite composite material; or it can be calculated as the weight of the zeolite loaded per unit area of ​​a planar matrix material.

[0005] The loading uniformity of a zeolite composite material refers to the uniformity of the zeolite component distribution at different locations within the composite material, specifically, the fluctuations in zeolite loading at different locations within the composite material. In the analysis and testing of zeolite loading and zeolite loading uniformity, loading measurement is fundamental, and uniformity assessment is based on the analysis of loading test results at different locations. High uniformity is defined when the zeolite loading at different locations fluctuates minimally, while poor uniformity is defined when the zeolite loading at different locations fluctuates significantly. Therefore, uniformity assessment necessarily involves multi-point loading measurements.

[0006] During the production process and final product testing, it is very important to quickly and accurately analyze the zeolite loading of zeolite composite products, as well as to analyze, test and evaluate the uniformity of zeolite loading at different locations of zeolite composite products. These are key indicators for quality control of such products.

[0007] At present, in actual production and literature reports, the main methods for determining the loading amount of zeolite in zeolite composite materials are as follows:

[0008] (1) Transmission electron microscopy (TEM) observation: This method can directly observe and evaluate the ultra-small micro-areas (<0.000001cm) on the imaging screen of the device. 2 ) range, and the uniformity of distribution of zeolite particles on the matrix material.

[0009] (2) Scanning electron microscope (SEM) observation: This method can directly observe and evaluate micro-areas (<0.0001cm) on the imaging screen of the device. 2 ) within the range of the amount of zeolite loaded on the matrix material, and the uniformity of the distribution of the zeolite particles on the matrix material.

[0010] (3) Elemental analysis using energy dispersive X-ray spectrometer (EDX): This method can quantitatively test and analyze the elements in a micro area (<0.000001cm 2 ) zeolite loading, and can be tested and evaluated by line scanning and surface scanning in micro-area (<0.0001cm 2 ) Zeolite loading uniformity.

[0011] (4) Elemental analysis using X-ray fluorescence spectrometer (XRF): This method can quantitatively determine the elemental content of a small area (0.001 cm 2 -1.0cm 2 ) The average loading of the samples within .

[0012] (5) Using ICP-OES (inductively coupled plasma optical emission spectrometry) and ICP-MS (inductively coupled plasma mass spectrometry), samples from small sampling points (<500 mg) were dissolved with strong acid and strong base, and the elemental composition of the sampling points was measured to calculate the loading amount.

[0013] (6) Chemical titration analysis: After the samples at the small area sampling points are dissolved with strong acid and strong alkali, the elemental composition of the sampling points is determined by chemical titration to calculate the average load of the small area sampling points.

[0014] (7) Thermogravimetric analysis (TGA): This method can quantitatively analyze the average loading of samples taken from a small area (generally less than 100 mg in total weight) by the method of calcination weight loss.

[0015] (8) The muffle furnace calcination weight method tests the average loading of bulk materials (sample weight is about 1 gram to 100 grams).

[0016] Among the various testing methods in the above-mentioned related technologies, (1) TEM and (2) SEM are only qualitative analysis methods; (3) EDX, (4) XRF, (5) ICP, (6) chemical titration and other elemental analysis methods require that the non-zeolite components in the composite material do not contain zeolite constituent elements such as silicon and aluminum, otherwise it is impossible to distinguish the element sources, resulting in the inability to determine the zeolite loading; (7) TGA analysis and (8) muffle furnace calcination require that the non-zeolite components in the composite material are materials that can be removed by calcination, such as cotton gauze materials, carbon materials, and organic polymer materials, and are only applicable to the analysis of some zeolite composite materials.

[0017] Among the methods listed above, the muffle furnace calcination weight method (8) can obtain the average loading of samples with a larger area, but it cannot provide any information on the loading uniformity in the area.

[0018] Except for the muffle furnace roasting weight method (8), all other methods can only obtain the loading information of a single point of a small area sampling point in one test. 2 The information on zeolite loading uniformity, that is, the information on the loading variation at different locations, requires the above methods to perform multi-point sampling at different locations, analyze the loading amount point by point in turn, and then use the loading amount information of these isolated points to statistically infer the loading uniformity information within the distribution area of ​​the product sampling points.

[0019] These traditional loading analysis methods require multi-point sampling and individual testing, and only statistical methods can be used to evaluate and analyze the uniformity of zeolite loading. However, they have the following problems:

[0020] (1) The sampling points are isolated and non-continuous, which brings the possibility of missing some special areas. The defect distribution of products and the change of load do not necessarily have a clear distribution pattern. Any sampling cannot avoid the possibility of missing some special areas.

[0021] (2) It is difficult to quickly find the two extreme values ​​of the highest load and the lowest load by manually selecting sampling points, and it is impossible to determine the upper and lower limits of load fluctuations through the test results of a few sampling points.

[0022] (3) Extremely time-consuming and expensive. Sampling a large number of samples and analyzing them one by one increases the analysis time and cost. In addition, most of the above methods require extremely expensive equipment to perform.

[0023] (4) Traditional methods take a long time to obtain test results and therefore cannot meet the requirements of online testing.

[0024] In summary, at present, the detection methods in the existing technology cannot achieve the detection accuracy greater than 1cm.2 The method is to rapidly and cost-effectively continuously measure the load uniformity of zeolite composite materials within a specific area without missing any hidden dangers. However, in actual industrial production, it is expected to quickly obtain the continuous fluctuation of the zeolite loading between different areas on the macro scale of the zeolite composite material, and to be able to directly observe with the naked eye or quickly measure with simple instruments and equipment to determine the zeolite loading and zeolite loading uniformity information of the macro-scale zeolite composite material product. Therefore, the present application provides a method for rapid detection and evaluation of the zeolite loading and zeolite loading uniformity in a zeolite composite material. Summary of the Invention

[0025] In order to solve the technical difficulties existing in the above-mentioned technologies, the present application provides a rapid detection and evaluation method for the zeolite loading and zeolite loading uniformity in zeolite composite materials that is fast, low-cost, and can be operated in parallel, and based on this method, develops an analysis technology for the continuous and complete loading uniformity information of the detection area; in particular, it provides a universal detection and evaluation method for the zeolite loading and / or zeolite loading uniformity on macroscopic zeolite composite materials with a scale of more than 1 square centimeter.

[0026] Specifically, the idea of ​​the new load detection method provided by this application can be described as follows:

[0027] In a multi-component system containing zeolite, the originally colorless zeolite microparticles are transformed into zeolite particles with a specific dark color by sequentially performing selective coloring operations and enhanced color development operations on the zeolite microparticles. The color of the non-zeolite components is not changed during the above-mentioned treatment process, thereby transforming the microscopic technical problem of zeolite loading determination into a macroscopic color depth analysis problem.

[0028] The present application provides a method for rapid detection and evaluation of zeolite loading and zeolite loading uniformity in a zeolite composite material, which is achieved through the following technical solutions:

[0029] A method for rapidly detecting and evaluating the zeolite loading amount and zeolite loading uniformity in a zeolite composite material comprises the following steps:

[0030] Step (1), selective coloring: using a colorable metal cation solution to selectively color the zeolite component in the zeolite composite material to be detected;

[0031] Step (2), color enhancement: using an enhanced color developer to perform an enhanced color development treatment on the zeolite composite material obtained after the selective coloring operation in step (1);

[0032] Step (3), detection and evaluation of zeolite loading and loading uniformity:

[0033] Detection and evaluation of zeolite loading: prepare 2-20 zeolite composite materials of the same type with known loading as standard samples, and process the standard samples in the same manner as steps (1) and (2). Use optical instruments to test the optical performance parameters of the standard samples, establish the relationship between the zeolite loading and the optical performance parameters, and obtain a working curve for quantitative testing of the loading; perform the same optical performance parameter test on the zeolite composite material to be tested obtained through the same steps (1) and (2), and evaluate the zeolite loading in the zeolite composite material to be tested based on the obtained results and the working curve;

[0034] The optical performance parameters include absorbance, absorptivity, reflectivity, whiteness, and grayscale value;

[0035] Detection and evaluation of zeolite loading uniformity, by analyzing the color depth difference at different positions of the zeolite composite material obtained in step (2) to detect and evaluate the zeolite loading uniformity within the sampling area;

[0036] The color depth difference analysis means includes:

[0037] (a) Qualitative judgment is made by directly observing the color depth of different areas of the sample with the human eye;

[0038] (b) using an optical instrument to test the optical performance parameters of different areas of the sample for quantitative detection and analysis; the optical performance parameters include absorbance, absorptivity, reflectivity, whiteness, and grayscale value.

[0039] The rapid detection and evaluation method of the present application can be used for online detection in production, and can also be used for offline detection.

[0040] The present application provides a method for rapid detection and evaluation of zeolite loading and zeolite loading uniformity in a zeolite composite material, which can be operated in parallel on a large area and multiple samples, and can simultaneously and synchronously perform selective coloring and enhanced color development processing on all points within all sampling areas of multiple samples, thereby achieving the purpose of completely continuous and complete analysis of zeolite loading uniformity information in all areas within the sampling area.

[0041] Preferably, the optical instrument includes an absorption spectrum tester, a reflection spectrum tester, a whiteness meter, a camera with a computer, and a color processing system. The optical performance parameters measured by the absorption spectrum tester are absorbance and absorptivity; the optical performance parameter measured by the reflection spectrum tester is reflectivity; the optical performance parameter measured by the whiteness meter is whiteness; the optical performance parameter measured by the camera with a computer is grayscale; and the optical performance parameter measured by the color processing system is grayscale value.

[0042] By adopting the above technical solution, a single test is fast and can provide load uniformity information for the sampling range in one test. The fastest result can be obtained in three minutes. Therefore, it can be applied to online sampling testing of continuous production lines, achieving the goal of quasi-real-time monitoring of production line products.

[0043] The selective coloring operation in step (1) is specifically as follows: immersing the zeolite composite material in a solution of colorable metal cations, and partially replacing the original cations in the zeolite pores with colorable metal cations through a chemical reaction. During this process, the non-zeolite components will not undergo obvious ion exchange chemical reactions with the colorable metal cations, ensuring that the colorable metal cations only selectively enter the zeolite components.

[0044] Furthermore, the selective coloring operation is to color only the zeolite material but not the matrix material.

[0045] By adopting the above technical solution,

[0046] The enhanced color development operation in step (2) is specifically as follows: the colorable metal cations introduced into the zeolite composite material after the selective coloring treatment in step (1) are chemically reacted with the enhanced color developer molecules, and an in-situ reaction is performed at the location of the colorable metal cations to generate a substance with a darker color than the colorable metal cations.

[0047] Furthermore, the color depth of a certain area in the zeolite composite material after the selective coloring and enhanced color development operation is positively correlated with the zeolite loading amount in the sample area.

[0048] Furthermore, the enhanced color development treatment in step (2) is as follows: the sample to be tested, which has been treated in step (1), is placed in an atmosphere containing a gaseous enhanced color developer for fumigation treatment, so that the colorable metal cations introduced into the zeolite composite material in step (1) react chemically with the enhanced color developer to generate a substance with a darker color.

[0049] In the technical solution provided by the present application, the zeolite composite material is first subjected to a two-step process of selective coloring and enhanced color development in sequence, selectively converting the colorless zeolite material into particles with a strong specific color without changing the color of the non-zeolite component, thereby establishing a correlation between the zeolite loading in different regions of the composite material and the optical properties of the visible light band exhibited by the different regions of the composite material on a macroscopic basis. After the above treatment, the color is dark in the area with a large loading, and light in the area with a small loading; in the area without zeolite loading, the color of the composite material does not change before and after the treatment. In other words, the present application selectively changes the optical properties of the zeolite particles, allowing us to use optical property analysis technology within the visible light band to detect the loading of the zeolite.

[0050] The core of this application is that the key technical difficulty in coloring or dyeing operations lies in selectivity, allowing the "colored" "dye" to undergo a strong physical or chemical reaction only with a specific component in the composite system. After dyeing, the dye is only present in the target component and does not change the original form and position of the component within the composite system. In other words, in addition to selectivity, dyeing must also be non-destructive, not changing the amount and form of the dyed component. Ordinary organic dyes generally easily react chemically with hydroxyl groups on the surface of fabrics and ceramic substrates. Zeolite surfaces also have a large number of active functional groups such as silanols, which are easy to react chemically with organic dyes. Therefore, if zeolite composite materials are dyed with organic dyes, the chromogenic functional groups of the organic dyes will be grafted onto the surfaces of both the zeolite and the substrate material, making selective coloring impossible. The calculation scheme provided in this application creatively utilizes the chemical reaction of ion exchange to achieve selective, non-destructive, and quantitative coloring of zeolite materials.

[0051] The colorable metal cations described in this application refer to soluble metal cations that can react with the color enhancing developer molecules to form dark-colored substances. Preferably, the colorable metal cations are selected from any one or more combinations of copper ions, iron ions, chromium ions, zinc ions, nickel ions, manganese ions, lead ions, silver ions, cadmium ions, cobalt ions, and mercury ions. These ions can form dark complexes with ammonia or form dark sulfides with sulfide ions.

[0052] In zeolite materials, silicon, aluminum and oxygen atoms are covalently bonded to form a negatively charged zeolite crystal framework, and positively charged cations exist in the pores of the crystal framework to balance the negative charge of the framework. The cations in zeolite are usually colorless main group alkali metal ions such as hydrogen ions, lithium ions, sodium ions, potassium ions, alkaline earth metal ions such as calcium ions and magnesium ions, or ammonium ions. These metal cations can migrate freely in the pores, giving the zeolite material a super strong cation exchange capacity. Immerse the zeolite material in a solution of colorable metal cations, such as Cr 3+ 、Mn 2+ 、Fe 2+ 、Fe 3+ 、Co 2 + 、Ni 2+ 、Cu + and Cu 2+The ion exchange reaction can replace one or more of the above-mentioned colored color-developing metal cations into the pores of the zeolite material through an ion exchange reaction. The colorless metal cations in the original zeolite are displaced and enter the ion exchange liquid. This changes the cationic composition in the zeolite. It should be noted that the metal ions involved in ion exchange are not necessarily limited to the metal ions themselves, but can also be hydrated ions formed by metal ions and water. In this application, no distinction is made between metal ions and hydrated ions formed by metals and water, and they are collectively referred to as certain metal ions.

[0053] After the colored colorable metal ions are exchanged into the zeolite crystals, the zeolite is transformed into a substance with a certain color. Since the other components in the zeolite composite material do not have strong cation exchange capacity, their composition is not affected during the soaking process, and therefore, their optical properties will not have observable changes. Therefore, the above-mentioned coloring operation is selected to achieve the purpose of selectively changing the color of the zeolite active components. It is a highly selective coloring process that only changes the zeolite without changing the matrix material. At the same time, during the ion exchange process, only the internal metal cations of the zeolite and the colorable metal cations in the solution undergo migration and exchange, which does not change the structure of the crystal skeleton of the zeolite material, nor does it change the morphology and existence position of the zeolite material. Therefore, this is also a coloring process that is completely harmless to the distribution and morphology of the zeolite.

[0054] During the selective coloring process, the exchange of cations within the zeolite and the colorable metal cations is a reversible chemical reaction. As long as the reaction time is sufficient and equilibrium is achieved, the extent of the cation exchange reaction occurring within the zeolite in different parts of the composite material is identical. In other words, the content of colorable metal cations is consistent for each zeolite particle. A consistent proportional relationship exists between the amount of colorable metal cations in different regions of the composite material and the amount of zeolite in those regions. By detecting the amount of transition metal ions using optical techniques, it can be linearly converted to the amount of zeolite corresponding to that location. Therefore, selective coloring through ion exchange also achieves a strictly quantitative and proportional coloring effect. This ability to achieve quantitative and proportional coloring is a significant advantage compared to coloring / dying technologies in other fields.

[0055] Preferably, the color enhancing developer is one of ammonia gas, ammonia water, hydrogen sulfide, and alkali metal sulfide solution.

[0056] Preferably, the alkali metal sulfide solution is one or more combinations of sodium sulfide solution, potassium sulfide solution, ammonium sulfide solution, and lithium sulfide solution.

[0057] The transition metal ions used as colorable metal cations in this application have a certain color. In theory, after the ion exchange operation, the color difference can be generated due to the difference in zeolite loading in different regions, which can be directly used for analysis. However, the extinction coefficient of these metal ions is very low and the light absorption capacity is not strong. Therefore, after the ion exchange coloring operation, the color of the zeolite is still relatively light, and the color difference between different loading regions is small, resulting in the following consequences: (1) the quantitative analysis error of the zeolite loading is large; (2) the minimum detectable loading requirement for low loading is high, and it is impossible to determine whether it is loaded after it falls below a certain value; (3) the contrast between high-load and low-load regions is not obvious. In order to improve the detection capability, reduce the analysis error, and increase the color contrast of different loading regions, the technical solution provided in this application also adds a further enhanced color development operation for the composite material after the coloring operation.

[0058] Specifically, the enhanced color development operation refers to the process of reacting a light-colored colorable metal ion with an enhanced color developer on a composite material after ion exchange to generate a substance darker than the colorable metal cation at the location of the colorable metal cation. The enhanced color development operation converts transition metal ions with a low extinction coefficient into substances with a high extinction coefficient through a chemical reaction to achieve an enhanced color development effect. The enhanced color developers selected in this application include but are not limited to ammonia (NH3), hydrogen sulfide (H2S) and sulfide ions, selenium ions, tellurium ions, etc. The chemical principles on which different enhanced color developers work are not completely consistent.

[0059] The enhanced color development function of ammonia (NH3) is because ammonia molecules can quantitatively form complex ions with a variety of color-developing metal ions. The reaction formula can be expressed as: n+ +xNH3→[M(NH3)x] n+ These complex ions have a higher extinction coefficient than the original metal ions, that is, the color of the complex ions formed by the same amount of color-forming metal ions and ammonia is many times darker than the color of the same amount of original color-forming metal ions. For example, copper ions (Cu 2+ ) has an extinction coefficient of 2.8 L mol -1 cm -1 , copper ammonia complex ion ([Cu(NH3)4] 2+ ) increases to 77 L mol -1 cm -1 , which is 27.5 times that of the original copper ion. It should be pointed out that not every colorable metal cation can form a complex ion with high light absorption capacity with ammonia.

[0060] Ammonia's enhanced color development can also come from the reaction of converting metal cations into metal hydroxides. During the ion exchange and gas fumigation process, water molecules exist in the zeolite pores in addition to the metal cations. During the ammonia fumigation process, ammonia enters the zeolite pores and reacts with the metal cations and water to form metal hydroxides and ammonium ions. The reaction equation can be expressed as:

[0061] M n+ +nNH3+nH2O→M(OH)n+nNH 4+ ; Hydroxides usually have better light absorption ability than the corresponding metal cations, thereby enhancing the color development effect.

[0062] In the actual color development process, both mechanisms may play a role. When there are no water molecules in the zeolite pores, hydroxide cannot be formed. When there are more water molecules in the pores, hydroxide may be formed first in the early stage, and then the excess ammonia molecules will convert the hydroxide into an ammonia complex. The reaction formula can be expressed as: M(OH) n +xNH3→+[M(NH3)x] n + +nOH - .

[0063] For some colorable metals, forming complexes with ammonia is more stable, thus enhancing color development through the first ammonia complex. Other colorable metals, forming hydroxide precipitates with hydroxide, are more stable, and when water is present in the pores, this hydroxide precipitate enhances color development. In specific applications, there is no restriction on which mechanism is used; as long as the product generated under the selected conditions has a higher extinction coefficient than the metal cation itself, the color enhancement effect can be achieved.

[0064] The enhanced color development function of hydrogen sulfide comes from the reaction between hydrogen sulfide and color-developing metal ions to produce metal sulfide. The reaction formula can be expressed as: n+ +(n / 2)H2S→M2S n / 2 +nH + The transition metal sulfide (M2S n / 2) are all semiconductor materials with a narrow band gap width, which can have a strong light absorption ability in the visible light band and a darker color. For example, copper ions react with hydrogen sulfide to form copper sulfide, which is a black substance. Lead ions and hydrogen sulfide react to form lead sulfide, which is also a black substance. Similarly, using hydrogen selenide / hydrogen telluride and transition metal ions to form selenide / telluride semiconductors can also enhance color development. Its reaction mechanism is similar to the reaction mechanism of hydrogen sulfide and colorable metal cations. However, hydrogen selenide, hydrogen telluride, etc. are expensive and more toxic, and the color enhancement effect is equivalent to that of hydrogen sulfide. Therefore, hydrogen sulfide is preferred in practical applications.

[0065] In addition to the above-mentioned colorable metal cations, there are also Zn 2+ , Pb 2+ 、Cd 2+ 、Hg 2+ Colorable metal cations that are inherently colorless can also be used in the application. After these cations are replaced into the zeolite through an ion exchange reaction, since these colorable metal cations are inherently colorless, they do not change the color of the zeolite. However, unlike the existing metal cations in the zeolite, such as potassium, calcium, and sodium, these colorless colorable metal cations can be easily converted into colored substances through a second step of enhanced color development, thereby achieving the same color development effect. For example, cadmium ions react with hydrogen sulfide to produce orange-yellow cadmium sulfide; mercury ions react with hydrogen sulfide to produce a black product; and lead ions react with hydrogen sulfide, hydrogen selenide, and hydrogen telluride to form black lead sulfide, lead selenide, and lead telluride.

[0066] In the present application, gas is preferably used as the actual enhancing color developer, and color enhancement is performed by gas fumigation. Try to avoid solution immersion operations. The reason is: to avoid ion migration during the operation, which may cause misjudgment. The colorable metal ions introduced into the zeolite in the first step of the selective coloring operation can migrate freely inside the zeolite. If they are immersed in a solution, they may be exchanged out and then migrate to other positions in the solution. Gas fumigation can limit the reaction between the colorable metal ions and the fumigant gas to the pores of the zeolite, ensuring that no position migration occurs during the second step of the treatment. The fumigant gas used in the enhanced coloring operation can be ammonia and hydrogen sulfide gas. However, other enhanced coloring molecules with similar functions, such as hydrogen selenide, hydrogen telluride, etc., are not excluded.

[0067] The gases used as color-enhancing agents are all somewhat toxic, so fumigation must be performed in a closed or semi-closed space. Fumigation can be performed by directly injecting the gases into the container containing the material, or by placing precursors that generate these gases in the container for an in-situ reaction. Hydrogen selenide, hydrogen telluride, and aqueous solutions of alkali metal selenides can achieve the same color-enhancing effect as hydrogen sulfide and sulfides, but they are far more toxic than sulfides and are more expensive, making them less practical.

[0068] For example, an aqueous ammonia solution can be used as a source of ammonia gas. Ammonia molecules evaporate from the solution, enter the pores of the zeolite, and form complexes with metal ions. Alternatively, calcium hydroxide and ammonium chloride solids can be mixed to produce ammonia molecules in situ. Similar reactions include sodium hydroxide and ammonium nitrate, calcium hydroxide and ammonium sulfate, and so on. Hydrogen sulfide can be supplied from a hydrogen sulfide gas cylinder or generated through a reaction.

[0069] For example, sodium sulfide aqueous solution plus hydrochloric acid, solid sodium sulfide plus dilute sulfuric acid, ferrous sulfide plus dilute hydrochloric acid, thiourea thermal decomposition, thioacetamide hydrolysis by adding water, and ammonium sulfide plus a non-oxidizing acid. Numerous reactions can produce ammonia and hydrogen sulfide, and the specific reactions that can be used in the present invention are not limited to the reactions listed above.

[0070] When the reaction speed between the color-forming metal and the color developer is fast enough, the enhanced color development operation can also be performed by solution immersion, and is not completely limited to the use of gas color developers.

[0071] For example, when a zeolite with a color-forming metal ion is immersed in a solution containing sulfur ions, such as sodium sulfide, hydrogen sulfide, or potassium sulfide, the color-forming metal will immediately react with the sulfur ions to form a dark sulfide precipitate, achieving an in-situ color development effect. When a zeolite with a trivalent iron ion is immersed in a solution of potassium thiocyanate or sodium hydrosulfide, it will immediately form a blood-red substance, achieving an in-situ color development effect.

[0072] From another perspective, the enhanced color development process is equivalent to performing a selective, quantitative, enhanced dyeing process after the composite material has already undergone a selective, quantitative dyeing process via ion exchange. This dyeing process selectively and quantitatively dyes the color-developing metal ions introduced into the zeolite after the initial dyeing process. This dual selective, quantitative dyeing process is a novel technique not previously reported in the art.

[0073] The new technology disclosed in this application introduces colorable metal cations, which were not originally present in the system, into the zeolite component during a first dyeing operation. Then, during a second dyeing operation, these introduced colorable metal cations are selectively converted in situ into a darker substance. The color developer (ammonia, hydrogen sulfide, etc.) used in the second dyeing cycle is inherently colorless and does not carry any chromophores. The principle of enhanced color development is that the color developer used in the second dyeing cycle chemically changes the electronic state of the colorable metal cations introduced in the first dyeing cycle, thereby deepening the color of the system.

[0074] Because the developer used in the second round of staining is inherently colorless, it does not alter the color or optical properties of the substrate. Furthermore, as long as the amount of enhanced developer added exceeds the amount required for the metal ion reaction, adding more will not cause further reactions or introduce additional color. Therefore, controlling the amount of enhanced developer added is extremely simple: simply ensure an excess, without worrying about the impact of the added amount on the quantitative test results.

[0075] In the actual application of the method provided by this application, it is very easy to determine whether the enhanced developer used in the second round of dyeing is excessive. In addition to the difference in depth, the color introduced by the metal ions in the first round of dyeing and the color after the second round of enhanced color development also have different colors.

[0076] For example, copper ions are light blue-green, but after ammonia fumigation, they turn blue-purple. The difference in color is very noticeable. Therefore, simply checking for the presence of blue-green patches in the sample can determine if ammonia fumigation has been adequately applied. Once sufficient ammonia is present, adding more will not affect the color. This is because the enhanced color development process is a specific chemical reaction, with the two reactants in a strict stoichiometric ratio. Both the reactants and the products have their own unique absorption peaks and colors.

[0077] In this application, the basis of the second round of dyeing is the substance introduced in the first round of dyeing; the newly added dye in the second round has no color itself, and the excess does not affect the test results. This is another innovative point of the technical solution provided by this application.

[0078] After the selective coloring and enhanced color development described above, we can analyze the sample's color depth and uniformity to obtain information about the zeolite loading and uniformity on the support. If a clear quantitative relationship between the two is required, a series of materials with different loadings can be synthesized as standards. After performing cation exchange under identical conditions, a working curve can be generated to determine the relationship between the material's absorbance or reflectance and the zeolite loading. For unknown samples, after the same coloring and enhanced color development conditions, the absorbance or reflectance can be measured and the loading of the unknown sample can be calculated using the working curve.

[0079] In the description of this application, selective ion exchange means that under the ion exchange reaction conditions adopted, although the carrier itself may also adsorb a certain amount of colorable metal cations, its adsorption amount is much lower than the adsorption amount produced by the zeolite through the ion exchange reaction. Therefore, the carrier's trace adsorption of colorable metal cations basically does not affect the evaluation of the zeolite loading distribution through color distribution.

[0080] For some real-world products, the carrier material may not be completely inert. The carrier material itself has a certain adsorption capacity for transition metal ions, which can cause color changes before and after ion exchange due to the adsorption of transition metal ions by the carrier material, causing interference. In these special cases, it is necessary to control conditions, such as the pH value of the ion exchange fluid, to achieve a more significant difference in the ion adsorption capacity of the carrier material and the zeolite material, thereby increasing the color difference after color development.

[0081] In addition, during data processing, the effect of carrier material adsorption can be eliminated by preparing a blank sample of the carrier material without loading to collect baseline data, and the effect of carrier adsorption can be eliminated in subsequent processing. As can be seen in the examples of this application, in most cases the effect of carrier adsorption is minimal and can be ignored.

[0082] The colorable metal ions selected for use in this application will be hydrolyzed and converted into hydroxides under higher pH conditions, forming flocculent precipitates. At this point, the color-developing metal no longer exists in the form of freely movable ions, and the ion exchange operation cannot be successfully completed. Therefore: it is necessary to carry out targeted control of the pH value of the ion exchange liquid so that the pH value must be less than the threshold value at which the metal ions precipitate as hydroxides. At the same time, the pH cannot be too low, because most zeolites such as zeolites can be partially dissolved in strong acid solutions, causing structural damage. The coloring process after structural destruction is no longer an in-situ reaction process. Therefore: the pH value control of the ion exchange solution must consider both the stability of the metal ions and the stability of zeolites such as zeolites at the pH value. Specifically, the lower limit of the pH value is determined by the stability of the zeolite, and generally, the stability of the zeolite can be guaranteed when it is higher than 2.0. The upper limit of the pH is determined by the stability of the ions in the solution:

[0083] Preferably, the colorable metal cation is selected from copper ions, and the pH value of the copper ion solution is below 6.5;

[0084] When the colorable metal cation is selected from iron ions, the pH value of the iron ion solution is below 3.5;

[0085] When the colorable metal cation is selected from chromium ions, the pH value of the chromium ion solution is below 5.8;

[0086] When the colorable metal cation is selected from zinc ions, the pH value of the zinc ion solution is below 7.5;

[0087] When the colorable metal cation is selected from nickel ions, the pH value of the nickel ion solution is below 7.4;

[0088] When the colorable metal cation is selected from manganese ions, the pH value of the manganese ion solution is below 9.8;

[0089] When the colorable metal cation is selected from lead ions, the pH value of the lead ion solution is below 8.0;

[0090] When the colorable metal cation is selected from silver ions, the pH value of the silver ion solution is below 9.5;

[0091] When the colorable metal cation is selected from cadmium ions, the pH value of the cadmium ion solution is below 8.0;

[0092] When the colorable metal cation is selected from cobalt ions, the pH value of the cobalt ion solution is below 8.0.

[0093] After the first selective coloring step and the second enhanced coloring step, the zeolite composite material contains more zeolite in areas with high loading. Consequently, more metal ions are exchanged into the zeolite in these areas. After the enhanced coloring process, the metal ions are converted into darker substances, resulting in a darker, more intense color in areas with high loading. Areas with low loading have a lighter color. Therefore, the loading can be judged by the depth of the color, and the color differences between different areas can be used to determine uniformity.

[0094] There are many ways to evaluate color, which does not affect the implementation of this application.

[0095] For example, in daily production, uniformity can be qualitatively assessed by direct visual observation. Many national and industry standards dictate the absence of noticeable color differences. Therefore, in this application, after selective quantitative coloring and enhanced color development, visual observation of noticeable color differences can be used as a qualitative assessment of whether the loading uniformity meets requirements.

[0096] Of course, it is also possible to use optical equipment to take photos / videos, then use software to automatically extract the color values ​​of different areas. Then, through customized processing, a quantitative uniformity index value is calculated to perform a quantitative assessment of uniformity. Colorimetry is another common semi-quantitative visual assessment method. If the uniformity meets the requirements, a series of samples with known loadings are pre-treated with the aforementioned selective coloring and enhanced color development procedures and used as standards of varying concentrations. The unknown sample is then subjected to the same ion exchange enhanced color development and compared with the standard sample itself, a photograph of the standard sample, or a color card with the same color depth as the standard sample to roughly semi-quantitatively determine the loading of the unknown sample. Colorimetry can also be automatically determined using an optical machine. Furthermore, optical equipment can be used to quantitatively measure the reflectance, absorbance, whiteness, and other quantitative values ​​of the standard sample to create a working curve. The loading of the unknown sample can then be calculated from the working curve using the reflectance, absorbance, whiteness, and other values ​​of the unknown sample, achieving rapid quantitative determination.

[0097] The present application utilizes a two-step chemical reaction of sequentially performing a selective coloring operation on the zeolite composite material to be tested and performing an enhanced coloring operation using a colorless enhanced color developer to obtain an effect having both high dyeing intensity and selective dyeing performance.

[0098] Preferably, the zeolite is selected from one or more combinations of A-type zeolite, X-type zeolite, chabazite, mordenite, faujasite, ZSM-5 zeolite, Y-type zeolite, P-type zeolite, and clinoptilolite zeolite; and the original cations in the zeolite are one or more combinations of hydrogen ions, lithium ions, sodium ions, potassium ions, calcium ions, magnesium ions, barium ions, and ammonium ions.

[0099] Zeolite is a general term for a large class of microporous aluminosilicate crystalline materials, primarily containing oxygen, silicon, aluminum, hydrogen, and alkali and alkaline earth metals such as sodium and calcium. Almost all synthetic zeolite materials themselves have no significant absorption capacity for light in the visible light band and therefore do not exhibit any color. Natural zeolites often contain trace amounts of transition metal impurities, which may result in a lighter color. In zeolite composites, zeolite is immobilized in the form of microscopic particles on a non-zeolite matrix material. The optical properties of regions where zeolite is present or absent, or where it is present in greater or lesser amounts, in the visible light band do not differ significantly from those of the macroscopic matrix material itself, making them indistinguishable to the naked eye or simple optical instruments. In the technical solution provided in this application, the zeolite composite material is first subjected to a two-step process of selective coloring and enhanced color development, selectively converting the colorless zeolite material into particles with a strong, specific color without changing the color of the non-zeolite components. This establishes a correlation between the zeolite loading in different regions of the composite material and the macroscopic optical properties of the different regions of the composite material in the visible light band. After this treatment, the color of the composite material becomes darker in areas with higher zeolite loading and lighter in areas with lower zeolite loading. In areas without zeolite loading, the color of the composite material remains unchanged. This means that by selectively altering the optical properties of zeolite particles, the present invention allows for the detection of zeolite loading using optical property analysis techniques within the visible light band.

[0100] Preferably, the zeolite composite material includes component A and component B, wherein component A is zeolite; component B is non-zeolite; component B is a matrix material or a loading substance of a matrix material plus other non-zeolite components; the matrix material includes textile products made of cotton fibers, textile products made of organic polymer fibers, and ceramic matrix material products; the textile products made of cotton fibers include gauze, non-woven fabrics, cotton cloth, and cotton balls; the textile products made of organic polymer fibers include non-woven fabrics, melt-blown fabrics, gauze, and cloth; the materials of the ceramic matrix material products include corundum, cordierite, and silicon carbide; the shapes of the ceramic matrix material products include flat plates, cylinders, round tubes, spheres, honeycomb ceramic structures, and ceramic fiber braids.

[0101] In summary, this application has the following advantages:

[0102] 1. The rapid detection method for zeolite loading provided by the present application can process multiple samples in parallel without sorting them one by one. Multiple samples can be selectively colored at the same time in the same container, and subsequently enhanced color development can be performed at the same time in the same container. There will be no mutual interference between the samples, and the evaluation effect will not be affected. Therefore, the use of standard samples to establish a working curve and process the test load of the samples to be tested can be completed simultaneously in the same processing container and the same batch operation can be completed simultaneously.

[0103] 2. The rapid zeolite loading uniformity assessment method provided in this application can achieve a comprehensive and rapid assessment of the loading amount and loading uniformity of the entire area of ​​a zeolite composite material of a larger area of ​​more than one square centimeter, or even as large as several square meters, and the assessment can be completed quickly within half an hour; the information obtained is completely continuous loading amount and load uniformity information within the entire sampling area. Compared with discrete point sampling detection, there is no possibility of missing special areas; while existing technical means can only obtain loading amount information of some discrete sampling points within the sampling area.

[0104] 3. The method provided in this application is easy to operate and does not require the use of large instruments and equipment.

[0105] 4. The enhanced color developer used in the second step of the enhanced color development operation of the present application is colorless in itself. Only after the enhanced color developer combines with the colorable metal cations inside the zeolite or other zeolites will it show a specific dark color. This ensures that the added enhanced color developer will not dye the base material and will not change the color of the base material itself. Therefore, excessive addition of the enhanced color developer will not change the enhanced color development effect. There is no need to precisely control the amount of enhanced color developer added, which is convenient for actual operation.

[0106] 5. Compared with other methods, the method used in this application has a fast single detection speed. One detection can provide load uniformity information of the sampling range, and the results can be obtained in as fast as three minutes. Therefore, it can be applied to online sampling detection of continuous production lines to achieve the purpose of quasi-real-time monitoring of production line products.

[0107] 6. In addition to being applicable to the evaluation of zeolite loading and uniformity in conventional zeolite composite materials, the method used in this application can also be applied to the quantitative determination of zeolite content in mixtures of zeolite powder and other powder materials. Like conventional composite materials, mixed powders contain both zeolite and other substances. The mixed powders can be subjected to selective coloring and enhanced color development procedures, with the zeolite component individually dyed. The zeolite content can then be calculated by observing and testing its optical properties, such as color depth, whiteness, and reflectivity and absorptivity at specific wavelengths of light. BRIEF DESCRIPTION OF THE DRAWINGS

[0108] Figure 1 The coloring effect of NaP zeolite powder after ion exchange in different metal nitrate solutions (first row), and the enhanced coloring effect after selective coloring treatment and fumigation with ammonia (second row) and hydrogen sulfide (third row).

[0109] Figure 2This is the coloring effect of NaP zeolite powder after ion exchange with nickel chloride, copper sulfate and mercuric chloride ions (first row), as well as the enhanced coloring effect after ammonia fumigation (second row) and hydrogen sulfide fumigation (third row).

[0110] Figure 3 The selective coloring effect of clinoptilolite, chabazite, faujasite and mordenite powders after ion exchange with copper sulfate and lead nitrate, respectively (first row), and the enhanced coloring effect after fumigation with hydrogen sulfide gas (second row).

[0111] Figure 4 The UV-visible spectrometer is used to test the diffuse reflectance spectra of zeolite powder, zeolite powder after copper ion exchange, zeolite powder after ammonia fumigation treatment and powder material after hydrogen sulfide fumigation treatment at light between 400 and 750 nanometers.

[0112] Figure 5 Color photos of zeolite-barium sulfate mixed powders with different proportions at different processing stages. The photos show that the higher the zeolite content, the darker the color after the two-step operation of selective coloring and enhanced color development.

[0113] Figure 6 This is the relationship between the weight percentage of zeolite in a zeolite-barium sulfate mixture and the whiteness of the mixture after silver ion exchange and hydrogen sulfide fumigation. The ordinate in the left graph is a linear axis, while the ordinate in the right graph is a logarithmic axis.

[0114] Figure 7 It is the corresponding relationship between the weight percentage of zeolite in the zeolite-alumina mixed powder and the whiteness of the mixed powder after silver ion exchange and hydrogen sulfide fumigation.

[0115] Figure 8 Photos of a zeolite-cordierite mixed powder and the mixed powder after copper ion exchange and ammonia fumigation treatment. The higher the zeolite weight ratio, the darker the color of the treated mixed powder.

[0116] Figure 9 It is the corresponding relationship between the weight percentage of zeolite in the zeolite-cordierite mixed powder and the reflectivity of the mixed powder to visible light with a wavelength of 500 nanometers after the mixed powder undergoes copper ion exchange and ammonia fumigation.

[0117] Figure 10 Photos of white absorbent cotton gauze and a composite material loaded with type A zeolite prepared using the white absorbent cotton gauze as a matrix material; photos of the two materials after dyeing with five organic dyes; and photos of the two materials after copper ion exchange and ammonia fumigation.

[0118] Figure 11These are photos of pure absorbent cotton without zeolite loading and zeolite absorbent cotton loaded with 21% X-type zeolite, as well as photos of the two samples after selective coloring with an aqueous copper sulfate solution at pH 4 and 8, respectively, and enhanced color development with ammonia fumigation.

[0119] Figure 12 (a) A composite material obtained by immobilizing X-type zeolite on white cotton cloth, (b) the selective coloring effect of the composite material after ion exchange with copper chloride solution, (c) the enhanced coloring effect of the composite material after ammonia fumigation after ion exchange, and (d) the enhanced coloring effect of the composite material after hydrogen sulfide fumigation.

[0120] Figure 13 The present invention relates to (a) a composite material obtained by immobilizing chabazite on a cotton gauze matrix material, (b) a composite material obtained by ion exchange with a silver nitrate aqueous solution, (c) an enhanced color development effect of the composite material after silver ion exchange and fumigation with hydrogen sulfide gas, and (d) an enhanced color development effect of the composite material after silver ion exchange and soaking in a sodium sulfide aqueous solution.

[0121] Figure 14 The invention relates to a composite material comprising (A) a non-woven fabric matrix material loaded with Y-type zeolite, (B) a cotton fabric matrix material loaded with chabazite, and (C) a gauze matrix material loaded with clinoptilolite, as well as their color development effects after exchange with different metal ions and after different enhanced color development treatments.

[0122] Figure 15 This is a composite material with a cotton gauze matrix immobilized with a mixture of type A zeolite and chabazite. The color development effect after ion exchange with a copper sulfate aqueous solution (a) and further fumigation with hydrogen sulfide (b).

[0123] Figure 16 (A) is a photo of a 30 wt% chabazite-cotton gauze composite material after ion exchange by soaking in a copper chloride aqueous solution; (B) is a photo of a 30 wt% chabazite-cotton gauze composite material after ion exchange and then fumigation with concentrated ammonia water. The average loading of the two pieces is (C) 12 wt% and (D)

[0124] Photo of a 13wt% chabazite-cotton gauze composite material after copper ion exchange and fumigation with concentrated ammonia.

[0125] Figure 17 This is a graph showing the relationship between the reflectance spectrum of the zeolite sample loaded on the cordierite ceramic substrate in the range of 400-750 nanometers and the loading amount.

[0126] Figure 18It is a picture of the original samples obtained by sampling simultaneously on three production lines and a picture of the samples after the three samples are colored and enhanced in parallel. It is used to quickly judge the load uniformity of the products on the production line and is used for production control needs. DETAILED DESCRIPTION

[0127] The present application is further described in detail below with reference to the accompanying drawings and examples.

[0128] Example

[0129] Example 1

[0130] The present invention discloses a method for rapidly detecting and evaluating the zeolite loading amount and zeolite loading uniformity in a zeolite composite material, comprising the following steps:

[0131] Step (1), selective coloring: using a colorable metal cation solution to selectively color the zeolite component in the zeolite composite material to be detected;

[0132] The selective coloring operation is as follows: the zeolite composite material is immersed in a solution of colorable metal cations, and the original cations in the zeolite pores are partially replaced with colorable metal cations through ion exchange chemical reaction. During this process, the non-zeolite components will not undergo obvious ion exchange chemical reaction with the colorable metal cations, ensuring that the colorable metal cations only selectively enter the zeolite component.

[0133] Step (2), color enhancement: using an enhanced color developer to perform an enhanced color development treatment on the zeolite composite material obtained after the selective coloring operation in step (1);

[0134] The enhanced color development operation is specifically as follows: the colorable metal cations introduced into the zeolite composite material after the selective coloring treatment in step (1) react chemically with the enhanced color developer molecules, and react in situ at the location of the colorable metal cations to generate a substance darker in color than the colorable metal cations;

[0135] More specifically, the sample to be tested after the treatment in step (1) is immersed in a solution containing an enhanced color developer or is fumigated in an atmosphere containing a gaseous enhanced color developer, so that the colorable metal cations introduced into the zeolite composite material in step (1) react chemically with the enhanced color developer to generate a substance with a darker color;

[0136] Step (3), detection and evaluation of zeolite loading and loading uniformity:

[0137] Detection and evaluation of zeolite loading: prepare 2-20 zeolite composite materials of the same type with known loading as standard samples. The processing of the standard samples is the same as steps (1) and (2). Use optical instruments to test the optical performance parameters of the standard samples, establish the relationship between the zeolite loading and the optical performance parameters, and obtain a working curve for quantitative testing of the loading; evaluate the zeolite loading in the zeolite composite material to be tested by performing color depth analysis on the zeolite composite material obtained in step (2);

[0138] The technical means of color depth analysis include:

[0139] (a) Colorimetric method: Directly observe and compare the color of the sample to be tested with the standard samples with different zeolite loadings by human eyes, and make a qualitative judgment based on the color depth comparison results;

[0140] (b) using an optical instrument to test the optical performance parameters of the standard sample, wherein the optical performance parameters include absorbance, absorptivity, reflectivity, whiteness, and grayscale value, and establishing a working curve between the zeolite loading and the optical performance parameters; at the same time, measuring the optical performance parameters of the sample to be tested, obtaining the loading value of the sample to be tested from the working curve constructed using the standard sample data, and making a judgment based on the comparison results of the working curve;

[0141] Detection and evaluation of zeolite loading uniformity, by analyzing the color depth difference at different positions of the zeolite composite material obtained in step (2) to detect and evaluate the zeolite loading uniformity within the sampling area;

[0142] The color depth difference analysis means includes:

[0143] (a) Qualitative judgment is made by directly observing the color depth of different areas of the sample with the human eye;

[0144] (b) using an optical instrument to test the optical performance parameters of different areas of the sample for quantitative detection and analysis; the optical performance parameters include absorbance, absorptivity, reflectivity, whiteness, and grayscale value.

[0145] Optical instruments include absorption spectrometer, reflection spectrometer, whiteness meter, camera with computer, and color processing system. Among them, the optical performance parameters measured by the absorption spectrometer are absorbance and absorptivity; the optical performance parameter measured by the reflection spectrometer is reflectivity; the optical performance parameter measured by the whiteness meter is whiteness; the optical performance parameter measured by the camera with computer is grayscale; and the optical performance parameter measured by the color processing system is grayscale value.

[0146] This example uses pure NaP zeolite powder material without matrix material as a standard sample to demonstrate the effects of selective coloring operation and enhanced color development operation.

[0147] In this embodiment, the metal precursors are all metal nitrates as the source of colorable metal cations in the selective coloring operation, including chromium nitrate, manganese nitrate, cobalt nitrate, nickel nitrate, copper nitrate, cadmium nitrate and lead nitrate.

[0148] The selective coloring operation in the specific step (1) is as follows: 2 g of NaP zeolite powder is placed in a certain amount of metal nitrate solution, stirred or shaken for 30 minutes, the zeolite powder after ion exchange is collected by filtration, and washed with deionized water to remove the metal nitrate solution outside the particles.

[0149] Specific operating conditions such as solution concentration, solution solvent, and solution quality are listed in Table 1.

[0150] Table 1 Experimental conditions used for ion exchange of seven samples in Example 1, and the colors after each step of treatment

[0151] serial number Colorimetric cationic solution After coloring Ammonia fumigation hydrogen sulfide fumigation 1 2000 g of 0.2 M chromium nitrate aqueous solution light blue blue-gray - 2 20 g of 6.0 M manganese nitrate aqueous solution Germanium Gray black - 3 40 g of 2.0 M cobalt nitrate solution (water + ethylene glycol = 4:1) Rose red Tan - 4 200 g 1.5 M nickel nitrate solution (water + ethanol = 1:1) light blue-green blue black 5 100 g 3.0 M copper nitrate methanol (water + methanol = 1:2) blue-green blue-purple black 6 400 g of 0.8 M cadmium nitrate aqueous solution light apricot - orange 7 800 g of 0.6 M lead nitrate aqueous solution White - black

[0152] After coloring, Figure 1 As shown in the first row, except for the sample treated with lead nitrate, the originally pure white zeolite powders were transformed into samples with the corresponding metal ion colors after the coloring operation.

[0153] In this embodiment, two enhanced color rendering operations are selected:

[0154] 1. Take half of the powder after coloring in step (1) and place it on a shelf in a sealed container. Add concentrated ammonia water to the bottom of the container. Ammonia gas evaporates from the concentrated ammonia water and forms complex ions with the colorable metal cations in the zeolite or generates hydroxide precipitation to enhance the color development effect. Figure 1 Shown in the second row.

[0155] 2. After the first step of coloring, take the remaining half of the powder and place it on a shelf in a sealed container. Then, introduce hydrogen sulfide gas into the container for fumigation. Hydrogen sulfide reacts with transition metal ions to form color-developing metal sulfides to enhance the color development effect. The color of the material obtained after different stages of treatment can be seen in the following table: Figure 1 .

[0156] from Figure 1It is clearly visible in the figure: after selective coloring, the NaP zeolite is transformed into a colored powder, but most of the material is lighter in color. After ammonia or hydrogen sulfide fumigation, the color deepens even further. Enhanced color development doesn't simply deepen the color; the type of color changes as well. This is because the enhanced color development process doesn't simply increase the amount of metal ions, but rather chemically converts them into substances with higher extinction coefficients. The active light-absorbing substances before and after the transformation are different, so in addition to the deepening of the color, the color itself also changes. For example, after copper ion exchange, the zeolite displays a light blue color, the color of the copper ions; after ammonia fumigation, it displays the bluish-purple color of the copper-ammine complex; and after hydrogen sulfide fumigation, it displays the black color of copper sulfide.

[0157] Example 2

[0158] The difference between Example 2 and Example 1 is:

[0159] This example uses pure NaP zeolite powder material without matrix material as a standard sample to demonstrate the effects of selective coloring operation and enhanced color development operation.

[0160] In this embodiment, the metal precursors selected from non-nitrates are used as the source of color-developing metal ions in the selective coloring operation, including nickel chloride, copper sulfate and mercuric chloride.

[0161] The selective coloring operation in the specific step (1) is as follows: 2.0 g of NaP zeolite powder is placed in 400 ml of a metal salt solution with a concentration of 0.5 mol / L, stirred for 20 minutes, and the ion-exchanged powder is collected by filtration.

[0162] In this embodiment, two enhanced color rendering operations are selected:

[0163] 1. The powder after ion exchange in step (1) is placed on a shelf of a sealed container, ammonium chloride is placed at the bottom of the container, and ammonia gas is generated by dripping a sodium hydroxide aqueous solution with a concentration of 2 mol / L to form complex ions with the color-developing metal ions or generate hydroxide precipitates to achieve the effect of enhancing color development.

[0164] 2. The powder after ion exchange in step (1) is placed on a shelf in a sealed container. A saturated sodium sulfide solution is added to the bottom of the container. Hydrogen sulfide gas is generated by dripping a 2 mol / L hydrochloric acid aqueous solution. The generated hydrogen sulfide gas reacts with the colorable metal ions to form colorable metal sulfides, thereby achieving an enhanced color development effect. The color of the material obtained after different stages of treatment can be seen in Figure 2 .

[0165] After zeolite is treated with nickel chloride solution, it changes from white to yellow-green, and then turns to blue-gray after ammonia fumigation; if hydrogen sulfide fumigation is used as a color enhancement after coloring, the zeolite turns to a darker black.

[0166] After the zeolite is treated with copper sulfide solution, its color changes from white to blue, and after being fumigated with ammonia, it turns to blue-purple.

[0167] Zeolite is treated with mercuric chloride solution to change its color from white to brown, and then further treated with hydrogen sulfide fumigation to further deepen its color to black.

[0168] The above experimental results show that, similar to Example 1, the ion exchange and subsequent enhanced color development operations can be successfully completed by selecting different color-developing metal salts, and the anions of the salts do not affect the results.

[0169] Example 3

[0170] The difference between Example 3 and Example 1 is:

[0171] This example uses four pure zeolite powder materials, namely clinoptilolite, chabazite, faujasite and mordenite, as standard samples to demonstrate the effects of selective coloring operation and enhanced color development operation.

[0172] In this embodiment, copper sulfate and lead nitrate are selected as metal precursors as sources of color-developing metal ions in the selective coloring operation.

[0173] The selective coloring operation in the specific step (1) is as follows: 5.0 g of zeolite powder is placed in 500 ml of a metal salt solution with a concentration of 0.5 mol / L, stirred for 15 minutes, and the ion-exchanged powder is collected by filtration.

[0174] In this embodiment, hydrogen sulfide treatment was selected as the enhanced color development operation. Specifically, the powder after ion exchange in step (1) was placed on a shelf in a closed container. 100 ml of a mixed aqueous solution of thiourea and thioacetamide with a concentration of 5% was added to the bottom of the container. 5 ml of hydrochloric acid with a concentration of 2 mol / L was added. The entire container was heated to 80°C to allow the two organic sulfur sources to decompose and produce hydrogen sulfide gas. The generated hydrogen sulfide reacted with the color-developing metal ions to form color-developing metal sulfides to achieve an enhanced color development effect. The specific experimental results are shown in Table 2. The color of the material obtained after treatment is shown in Table 2. Figure 3 .

[0175] Table 2 Zeolite types in Example 3, colorable metal cation solutions, and colors after coloring and enhanced color development

[0176] serial number Zeolite varieties Colorable metal cation solution After coloring After enhanced color 1 Clinoptilolite 0.5 mol / L copper sulfate aqueous solution blue-gray Black and green 2 chabazite 0.5 mol / L lead nitrate aqueous solution White black 3 Faujasite 0.5 mol / L copper sulfate aqueous solution light blue black 4 Mordenite 0.5 mol / L lead nitrate aqueous solution light apricot black

[0177] Combine Figure 3As can be seen from Table 2, all zeolite materials exhibit excellent color development. After the enhanced color development treatment, clinoptilolite turns dark green, while chabazite, faujasite, and mordenite all turn black due to the conversion of metal ions into metal sulfides.

[0178] Example 4

[0179] The difference between Example 4 and Example 1 is:

[0180] This example uses NaP zeolite and faujasite powder materials to demonstrate the quantitative effects of coloring and color enhancement operations on the color and optical properties of the materials.

[0181] In this embodiment, reflectivity is used as an indicator of optical properties, and this value can also be converted into other optical properties such as absorbance, light absorption, etc. The reflectivity test instrument is a UV-visible spectrometer.

[0182] The selective coloring and enhanced color development treatments of the two zeolites are as follows:

[0183] Selective coloring: Use 5% copper sulfate aqueous solution as the coloring cation exchange liquid for coloring operation. After stirring for 30 minutes, filter and recover the powder.

[0184] Enhanced color development: A portion of the powder that has been selectively colored was treated with ammonia fumigation for 30 minutes as an enhanced color development operation; another portion of the colored powder was treated with hydrogen sulfide fumigation for 30 minutes as an enhanced color development operation; then, a UV-visible spectrometer was used to test the diffuse reflectance spectra of the original zeolite powder, the zeolite powder after copper ion coloring, the powder material after ammonia fumigation, and the powder material after hydrogen sulfide fumigation at 400-750nm. The test results are shown in Figure 4 .

[0185] See also Figure 4 , Figure 4 There are four curves in the NaP zeolite detection diagram, which represent the zeolite raw material, the zeolite powder after copper ion coloring treatment, the powder material after ammonia fumigation treatment, and the powder material after hydrogen sulfide fumigation treatment from the top to the bottom of the Y axis.

[0186] See also Figure 4 , Figure 4 There are six curves in the faujasite zeolite detection diagram, which represent zeolite raw material, zeolite powder after copper ion coloring treatment (dry), powder material after ammonia fumigation treatment (dry), zeolite powder after copper ion coloring treatment (wet), powder material after ammonia fumigation treatment (wet), and powder material after hydrogen sulfide fumigation treatment from top to bottom on the Y axis.

[0187] Before treatment, the reflectivity of both zeolite raw materials in this wavelength range was close to 100%, indicating that the bulk material basically did not absorb any light and the material appeared pure white. When the material was ion-exchanged with copper sulfate solution, the sodium ions in the material were partially replaced with copper ions, and the material changed from white to light pink-green. Figure 4 The reflectance spectrum shows a reflection peak between 450 and 550 nm. After ammonia fumigation, the material's reflection peak is around 425 nm, and the reflectance between 425 and 750 nm decreases significantly, indicating a significant increase in the material's light absorption capacity. This result is consistent with the visual observation of the material's color changing from light green to dark blue-purple. Furthermore, after hydrogen sulfide fumigation, the material strongly absorbs light across the entire 400-750 nm wavelength range, with an overall reflectance below 5%, consistent with the material's deep black color after hydrogen sulfide fumigation.

[0188] See also Figure 4 In the faujasite test image, it's important to note that the reflectance values ​​obtained under dry and wet conditions differ significantly. Wet conditions result in stronger absorption, darker color, and lower spectral reflectance. This is because the water film on the surface of the material under wet conditions reduces reflectivity, effectively increasing transmittance.

[0189] From Figure 4 The faujasite detection diagram clearly shows the overall offset of reflectivity under dry and wet conditions. Therefore, in actual application, the method of this application can achieve better observation results when observed under wet conditions. This example shows that the color depth evaluation analysis described in this application can be qualitatively analyzed by visual observation, or can be characterized and analyzed by quantitative values ​​such as the reflectivity / absorbance / transmittance of the material using optical equipment.

[0190] Example 5

[0191] The difference between Example 5 and Example 1 is:

[0192] Standard samples: Pure white 4A zeolite powder and pure white barium sulfate powder were mixed in varying proportions to prepare 14 samples, with zeolite content ranging from 0%, 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, and 100% by weight. 0% indicates the powder contains only barium sulfate, and 100% indicates the powder contains only zeolite. Both are white, making it impossible to directly distinguish the presence of zeolite and the proportion of zeolite in the mixture after mixing.

[0193] The selective coloring and enhanced color development treatments of the two zeolites are as follows:

[0194] Selective coloring: 10 g of the mixture sample was mixed with 500 ml of a 0.5 mol / L silver nitrate aqueous solution and stirred for 6 hours. Several drops of nitric acid were added to the silver nitrate aqueous solution to make the solution acidic, with a pH between 4 and 5.5, and in this embodiment, the pH value was 4.8. After stirring, the powder was filtered and collected. The powder was rinsed with ultrapure water until no white precipitate was produced when the eluent was added to a 1 mol / L sodium chloride aqueous solution. The powder was then dried and placed in a plastic petri dish. Figure 5 After silver ion exchange, the mixture of barium sulfate and zeolite powder still appears white, and there is no difference in the appearance of samples with different zeolite contents.

[0195] The enhanced color development operation is specifically performed as follows: all powder samples after ion exchange in step (1) are placed side by side on a shelf in a sealed container, 200 ml of a 10% sodium sulfide aqueous solution is added to the bottom of the container, and 100 ml of a 2 mol / L dilute sulfuric acid solution is slowly added. The generated hydrogen sulfide reacts with the color-forming metal ions to form color-forming metal sulfides to achieve an enhanced color development effect. The mixture is fumigated in a hydrogen sulfide atmosphere for 1 hour. See [Referring to] Figure 5 , we can see that after hydrogen sulfide fumigation, the zeolite-containing sample becomes noticeably darker, with higher zeolite content indicating darker color. A mixture of barium sulfate and 4A zeolite powders of unknown proportions can be treated in the same manner as above, undergoing silver ion exchange and hydrogen sulfide fumigation, followed by comparison with the aforementioned standard sample to determine the zeolite content.

[0196] In addition, we use a whiteness measuring instrument to test the whiteness of the powder. The obtained whiteness value can be directly used as a quantitative indicator to draw a working curve. Figure 6 , we can see that if the vertical coordinate whiteness value is plotted using logarithmic coordinates ( Figure 6 The data points in the region of zeolite content between 5% and 80% have good linear correlation and can be used as a working curve.

[0197] The test sample is a sample with a zeolite content of 27.5%. It is subjected to the same silver ion coloring operation and hydrogen sulfide fumigation enhancement coloring operation as in this embodiment, and then its whiteness value is tested. Figure 6 The zeolite content was found on the working curve in the right figure. The zeolite content found was 28.6%, which is relatively consistent with the actual value of 27.5%. This shows that the detection and evaluation method provided in this application can be used to determine the proportion of zeolite in a mixture of zeolite and other powders.

[0198] Example 6

[0199] The difference between Example 6 and Example 1 is that:

[0200] Standard samples: Pure white chabazite powder and light alumina powder were mixed in varying proportions to prepare 12 samples, with zeolite content ranging from 0%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, and 100% by weight. 0% indicates the powder contains only alumina, while 100% indicates the powder contains only zeolite. Both samples are white, making it impossible to directly distinguish the presence of zeolite and the proportion of zeolite in the mixture after mixing.

[0201] The selective coloring and enhanced color development treatments of the two zeolites are as follows:

[0202] Selective Coloring: Mix 10 g of the mixture with 400 ml of a 1 mol / L aqueous silver nitrate solution (pH 5.5) and stir for 2 hours. Filter and collect the powder, rinse with ultrapure water until no white precipitate forms when the eluent is added to a 1 mol / L aqueous sodium chloride solution. Dry and place in a plastic Petri dish. After silver ion exchange, the mixture of alumina and zeolite powder remains white, with no difference in appearance between samples with different zeolite contents.

[0203] Enhanced color rendering operation, specifically the following operations:

[0204] All the powders after ion exchange in step (1) are placed side by side on a shelf in a closed container, 200 ml of a 10% sodium sulfide aqueous solution is added to the bottom of the container, and 100 ml of a 2 mol / L dilute sulfuric acid solution is slowly added. The generated hydrogen sulfide reacts with the color-developing metal ions to form color-developing metal sulfides to achieve an enhanced color development effect, and the mixture is fumigated in a hydrogen sulfide atmosphere for 1 hour.

[0205] After hydrogen sulfide fumigation, the sample containing zeolite becomes obviously black. The higher the zeolite content, the darker the color. The whiteness of the above powder is tested using a whiteness meter. The obtained whiteness value is plotted against the weight percentage of zeolite in the mixed powder to obtain the following: Figure 7 The data shown.

[0206] See also Figure 7 , it can be seen that: within the entire range of different zeolite contents, when the whiteness values ​​are plotted on a logarithmic scale, the whiteness values ​​and the zeolite content show a good linear correlation. It can be seen that in this embodiment, due to the low density of the light alumina powder, the volume share is high at the same weight ratio. Therefore, under the same zeolite weight ratio, the whiteness of this series of samples (light alumina + zeolite) is significantly higher than the whiteness of the series of samples in Example 5 (barium sulfate + zeolite). This result suggests that for the determination of the zeolite content in different mixtures, it is necessary to independently prepare standard samples for the specific mixture and draw a working curve, which can then be used for the quantitative determination of the zeolite content in that particular type of mixture.

[0207] In this example, five mixtures of alumina and zeolite powders with different ratios were prepared as test samples to verify the effectiveness of the method. The proportions of zeolite in the five samples were 23.0%, 35.5%, 42.5%, 55.0%, and 69.0%, respectively. After these five samples were subjected to the same ion exchange and hydrogen sulfide fumigation treatment as in this example, their whiteness values ​​were tested. Figure 7 The corresponding zeolite ratios were read from the working curve shown, and the values ​​obtained were 23.9%, 33.8%, 43.0%, 55.6%, and 67.5%, respectively, which were within 2.0% of the actual feed ratio, proving the effectiveness of the above method.

[0208] It should be pointed out that different whiteness meters use light sources of different wavelengths. The same sample may give different whiteness values ​​on different whiteness meters. Therefore, the calibration of the above working curve and the measurement of actual samples need to be carried out on the same whiteness meter.

[0209] Example 7

[0210] The difference between Example 7 and Example 1 is that:

[0211] Standard samples: Pure white P-type zeolite powder and white cordierite powder were mixed in different proportions to prepare 12 samples, with the weight percentage of zeolite being 0%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, and 100%. 0% indicates that the powder contains only cordierite, and 100% indicates that the powder contains only zeolite. Figure 8 Before copper ion exchange, all mixtures of cordierite and zeolite powders were pure white. There was no difference in appearance between samples with different zeolite contents. After mixing, it was impossible to directly distinguish whether there was zeolite in the mixture and the proportion of zeolite.

[0212] The selective coloring and enhanced color development treatments of the two zeolites are as follows:

[0213] Selective coloring: Mix 10 g of the mixture with 500 ml of a 2 mol / L copper sulfate aqueous solution with a pH of 5.0 and stir for 15 min. After stirring, filter and collect the powder, rinse three times with ultrapure water, and then directly place it into a plastic petri dish in a wet state.

[0214] The enhanced color development operation is specifically as follows: all powder samples after ion exchange in step (1) are placed side by side on a shelf in a sealed container, 50 ml of concentrated ammonia water with a concentration of 25-28% is added to the bottom of the container, and the ammonia gas volatilized from the ammonia water reacts with the copper ions in the zeolite to generate dark-colored copper ammonia complex ions, achieving an enhanced color development effect, and fumigation treatment is carried out in an ammonia atmosphere for 1 hour. Figure 8After 1 hour of copper ion exchange and ammonia fumigation treatment, the sample containing zeolite turned obviously blue-purple. The higher the zeolite content, the darker the color.

[0215] The reflectivity of the powder at a wavelength of 500 nm was measured using an ultraviolet-visible spectrometer, and the reflectivity value obtained was plotted against the weight percentage of zeolite in the mixed powder to obtain the following: Figure 9 The data shown.

[0216] See also Figure 9 It can be seen that when the zeolite content is between 5% and 90%, the reflectivity value and the zeolite content show a good linear correlation. This indicates that the method provided in this application is suitable for rapid determination of the zeolite content in a zeolite powder mixture.

[0217] It should be noted that the above fumigation operation can fumigate multiple samples simultaneously and process them in parallel, so the establishment of the working curve and the determination of multiple unknown samples can be carried out simultaneously without having to process them one by one.

[0218] Example 8

[0219] The difference between Example 8 and Example 1 is that:

[0220] In this embodiment, a degreased cotton gauze original material without any zeolite component and a zeolite-cotton gauze composite material loaded with 18% type A zeolite prepared using the degreased cotton gauze as a matrix were selected as comparative samples to detect their differences in different coloring / dying processes.

[0221] See also Figure 10 Before any treatment, use absorbent cotton gauze ( Figure 10 a) and zeolite-loaded composite materials ( Figure 10 b) There is no discernible difference in appearance, all are uniform white gauze.

[0222] See also Figure 10 , and dyed them with five common textile industry dyes. After washing, it was found that the absorbent cotton gauze raw material and the zeolite-cotton gauze composite material were dyed the same rose red by organic dyes ( Figure 10 c, d), yellow-green ( Figure 10 e, f), Cuilan ( Figure 10 g, h), indigo ( Figure 10 i, j) and purple ( Figure 10 There is no visible difference between the two after dyeing, and it is impossible to distinguish whether there is zeolite on the material, which means that ordinary organic dyes cannot selectively color the zeolite material.

[0223] According to the method provided in this application, selective coloring and enhanced color development are performed:

[0224] Selective coloring: 10g of each material was soaked in 700ml of 1mol / l copper sulfate pentahydrate solution with a pH of 5.0 for 15 minutes for selective coloring. After the ion exchange in the selective coloring was completed, the two materials were rinsed three times in tap water to remove the copper ions that were not in the zeolite crystals of the material. Figure 10 , you can see that the absorbent cotton gauze without any zeolite still appears pure white ( Figure 10 m), which is no different from the original state. The zeolite-cotton gauze composite material turns light blue-green ( Figure 10 This color is the color of copper ions, indicating that it is the loaded zeolite, not the cotton gauze base material, that has absorbed the copper ions. This means that copper ions can selectively bind to the zeolite through ion exchange, turning the zeolite a light blue-green color.

[0225] Enhanced color development: Place the two materials after the above coloring treatment in a sealed container at the same time, and use 20 ml of concentrated ammonia water to volatilize ammonia and fumigate for 15 minutes. Figure 10 The last column shows the original absorbent cotton gauze material after the selective coloring and enhanced color development, which still appears pure white ( Figure 10 o), because there is no copper ion adsorption, the second step of ammonia fumigation operation has no effect on it.

[0226] refer to Figure 10 The last column, the composite material loaded with type A zeolite, changed from light blue-green to dark blue after ammonia fumigation ( Figure 10 p). Because ammonia changes the copper ion in the zeolite into the copper ammonia complex ion of dark blue color.In the processing of this sample, the first step is selectively bonded to the copper ion on the zeolite by ion exchange, and does not act with the cotton gauze base material.Then after the second step ammonia fumigation treatment, the copper ion selectively is quantitatively changed to the dark color copper ammonia complex ion, so that zeolite has strong dark blue, and the existence of zeolite can be observed easily.And the zeolite-cotton gauze composite material color is uniform after processing, and illustrates that zeolite is evenly distributed on the gauze base material.

[0227] This embodiment demonstrates that the method provided in the present application can selectively color zeolite and selectively enhance the color-developing metal ions introduced in the first step of the color development operation without changing the optical properties of the matrix material, so that the treated sample can be simply analyzed and identified by macroscopic naked eye observation or optical equipment to identify the existence and distribution state of microscopic colorless zeolite particles on the macroscopic base material that were originally unable to be directly observed.

[0228] Example 9

[0229] The difference between Example 9 and Example 1 is that:

[0230] A zeolite-absorbent cotton composite material loaded with X-type zeolite was synthesized using medical absorbent cotton as raw material, with the zeolite content being about 21%.

[0231] Two samples, each weighing 5.0 grams, were taken from a raw medical absorbent cotton material (labeled as pure cotton material) that did not contain zeolite. Each sample was placed in a glass beaker containing 700 mL of a 2-M copper sulfate solution. The pH of the first beaker was adjusted to 4.0 ± 0.2 with 0.1 M sulfuric acid solution; the pH of the second beaker was adjusted to 8.0 ± 0.2 with 0.1 M sodium hydroxide solution. After shaking for 3 hours, the samples were removed, rinsed twice with tap water, and then fumigated with 20-25% aqueous ammonia at room temperature for 1 hour.

[0232] Two samples, each weighing 5.0 g, were taken from a zeolite-wool composite material containing 21% X-type zeolite (labeled as zeolite wool material). The two samples were placed in glass beakers containing 700 mL of a 2-mol copper sulfate solution as above. The pH value of the first beaker was adjusted to 4.0±0.2 with 0.1-mol sulfuric acid solution; the pH value of the second beaker was adjusted to 8.0±0.2 with 0.1-mol sodium hydroxide solution. After shaking for 3 h, the samples were removed, rinsed twice with tap water, and then fumigated with ammonia water at room temperature for 1.0 hour.

[0233] See the photos of the four samples before and after treatment. Figure 11 As shown, at a pH of 4, the absorbent cotton without zeolite remains white, indicating that even after soaking in a copper ion solution and fumigating with ammonia, the color remains essentially unchanged, indicating that the absorbent cotton substrate is not dyed. However, after the aforementioned treatment, the zeolite-containing zeolite cotton substrate displays a bluish-purple color, indicating that the zeolite component has been dyed bluish-purple. At a pH of 8, both the absorbent cotton without zeolite and the zeolite-containing zeolite cotton substrate turn bluish-purple after the aforementioned treatment, making it impossible to determine the zeolite content. This is because at a pH of 8, the copper ion solution used for selective coloring is converted into a copper hydroxide suspension. The copper ions are precipitated as copper hydroxide colloids, which are no longer able to participate in ion exchange. Furthermore, these colloids adsorb onto the surface of the absorbent cotton substrate, causing the absorbent cotton substrate to also absorb a large amount of copper. After ammonia fumigation, the copper hydroxide is converted into a bluish-purple copper ammonia complex. Therefore, at a pH of 8, selective coloring is unattainable, making it impossible to use the color of the treated substrate to assess zeolite loading. This embodiment illustrates that controlling the pH value of the metal ion solution used for coloring is also a necessary operating condition for the implementation of this application.

[0234] Example 10

[0235] The difference between Example 10 and Example 1 is that:

[0236] In this example, an unevenly distributed sample of zeolite powder in a striped pattern on a fabric substrate was intentionally synthesized and used as a standard sample to demonstrate the effects of selective coloring and enhanced color development.

[0237] The base material is ordinary white cotton cloth, 30 cm high, 100 cm wide, and 3000 cm2 in area. The loaded zeolite is X-type zeolite, which is distributed in stripes on the cloth carrier. The zeolite loading in different stripes is not strictly consistent. Since the zeolite and the base cloth are both white, there is no obvious visible difference between different parts in the photos before the product is colored. Figure 12 a).

[0238] According to the method provided in this application, selective coloring and enhanced color development are performed:

[0239] Selective coloring: Use 2 mol / L copper chloride aqueous solution as the color cation exchange solution, add hydrochloric acid to the copper chloride aqueous solution, adjust the pH value to between 5.0-6.0, soak 20 grams of fabric in 2 liters of copper chloride aqueous solution for 15 minutes, take out and wring out, then soak and rinse twice with deionized water, and dry at room temperature. Figure 12 , you can see that the fabric is very light green, and you can see slight differences in color in different parts, showing a light striped pattern ( Figure 12 b).

[0240] Enhanced color: Place the fabric on a shelf in a sealed container, add 20 grams of concentrated ammonia water to the bottom, and fumigate for 15 minutes. Figure 12 , take out the cloth, and you can clearly see that the color changes from light green of copper ions to dark blue purple of copper ammonium complex ions ( Figure 12 c) The stripe structure and the difference in color depth within the stripes can be clearly seen on the fabric. Compared with before ammonia treatment, the color contrast of different parts has been significantly enhanced.

[0241] Enhanced color development: Air dry the fabric, place it in a sealed container and fumigate it with a mixture of nitrogen and hydrogen sulfide. Remove it after 15 minutes of fumigation. Figure 12 , you can see that the purple of the copper ammonium complex ion turns into the black of copper sulfide ( Figure 12 d). Figure 12 The green, purple, and black streaks and distinct color differences are consistent with the zeolite loading distribution of the material, demonstrating the effectiveness of the color development operation and enhanced color development treatment.

[0242] No existing technology can provide such comprehensive information on the variation in striped zeolite loading over an area of ​​several thousand square centimeters through a single analysis. Using multi-point micro-area sampling and analysis would likely require collecting hundreds or thousands of data points to create a rough picture of the zeolite loading distribution. However, the method provided in this application enables rapid testing.

[0243] Example 11

[0244] The difference between Example 11 and Example 1 is that:

[0245] In this example, similar to Example 10, a sample with an uneven distribution of zeolite powder in stripes on a fabric substrate was artificially synthesized to serve as a standard sample to demonstrate the effects of selective coloring and enhanced color development. The substrate material was ordinary white cotton gauze, and the loaded zeolite was chabazite. The zeolite was distributed in stripes on the fabric carrier, and the zeolite loading in different stripes was not strictly consistent. Figure 13 , since both the zeolite and the base gauze material are white, no obvious visible difference can be seen in the different parts of the photo ( Figure 13 a).

[0246] According to the method provided in this application, selective coloring and enhanced color development are performed:

[0247] Selective coloring: Use 0.2 mol / L silver nitrate aqueous solution as the ion exchange solution. Soak the fabric in the silver nitrate aqueous solution for 15 minutes, remove it, wring it out, and soak it in fresh silver nitrate aqueous solution for another 15 minutes. Then rinse it twice with deionized water and dry it at room temperature. Figure 13 Since silver ions are colorless, there is no obvious color difference between the gauze before and after ion exchange ( Figure 13 b).

[0248] Enhanced color development: Place the fabric on a shelf in a sealed container, add ferrous sulfide powder to the bottom, slowly add dilute sulfuric acid to produce hydrogen sulfide, and seal for 15 minutes. Figure 13 , take out the cloth, you can clearly see the black stripes produced by silver sulfide, and the difference in color depth within the stripes ( Figure 13 c) The darker the area, the higher the zeolite loading, and the lighter the area, the lower the zeolite loading.

[0249] Gas fumigation is used primarily to avoid the effects of ion migration, but for reactions that rapidly form precipitation, color enhancement can also be performed in solution.

[0250] In this example, a similar zeolite material with striped distribution was prepared. After the same silver ion exchange operation, the material was washed, dried, and then quickly immersed in a 2 mol / L sodium sulfide aqueous solution. After reacting for ten minutes, it was taken out and washed with deionized water. Figure 13 ,from Figure 13 As can be seen from the above, a good color rendering effect can also be obtained, forming a clear black stripe pattern ( Figure 13 d). Figure 13 The dark streaks and distinct color differences in the image are consistent with the zeolite loading distribution of the material, demonstrating that gas fumigation and solution immersion are equally effective treatments for this material.

[0251] Example 12

[0252] The difference between Example 12 and Example 1 is that:

[0253] In this embodiment, similar to Embodiment 10 and Embodiment 11, three materials with stripe-shaped support structures were synthesized, such as Figure 14 As shown, (A) non-woven carrier material loaded with Y-type zeolite stripe structure; (B) cotton carrier loaded with chabazite stripe structure; (C) gauze carrier loaded with clinoptilolite stripe structure.

[0254] Among them, 20 grams of material A was immersed in a 1:1 mixed solution of methanol and water with a concentration of 5% cobalt acetate for half an hour for selective coloring operation, and then fumigated with concentrated ammonia water to volatilize ammonia for 1 hour for color enhancement treatment.

[0255] Among them, 20 grams of material B was immersed in a 5% copper nitrate aqueous solution for half an hour for selective coloring, and then fumigated with hydrogen sulfide gas for 1 hour for color enhancement treatment.

[0256] Among them, 20 grams of C material was soaked in a 5% lead nitrate aqueous solution for half an hour for selective coloring, and then soaked in 500 grams of a 1% ammonium sulfide aqueous solution as a color enhancement treatment method.

[0257] Photos of the three materials at different stages Figure 14As shown in the figure, the samples of copper nitrate and cobalt acetate after selective coloring treatment have very light color stripes that can show the strip structure of zeolite loading, but it is not very obvious. The sample after lead nitrate treatment, because the lead ion itself is also colorless, can not see the difference from the original sample, and the strip distribution characteristics of zeolite distribution can not be identified. After the three samples are subjected to their own color enhancement treatment, the sample with cobalt ion as the colorable metal cation shows an obvious purple-red stripe structure, and the sample with copper ion and lead ion as the colorable metal cation shows an obvious black stripe structure. In these treated samples, the area with obvious color is the area with relatively large zeolite loading, and the light-colored area is the area without basically zeolite loading. Its stripe structure is consistent with the distribution form of zeolite. The above results prove that after being treated by the method described in the technical solution provided by the application, the load distribution of zeolite on the matrix material can be directly observed, and the distribution form and load uniformity of zeolite can be judged.

[0258] Example 13

[0259] The difference between Example 13 and Example 1 is that:

[0260] The zeolite composite material in this example is a sample from the ZN zeolite gauze production of Feixin Innovation Materials Technology Co., Ltd., with a carrier made of absorbent cotton gauze. Both the carrier material and the loaded zeolite in the original sample are white. Six 0.5m x 0.5m samples were taken from different locations within the roll and analyzed using a muffle furnace roasting method to measure the ash weight. The results showed that the average zeolite loadings at these six sampling locations were 15.8, 14.9, 16.7, 16.5, 15.0, and 15.2 wt%, respectively. This indicates that the sample loadings are highly uniform and consistent across a larger scale. SEM analysis results indicate that the loaded zeolite is a mixture of type A zeolite and chabazite, with the ratio of the two zeolites varying little across different regions, consistently around 3:1. However, SEM observations and EDX microanalysis indicate significant variations in loadings at sub-millimeter scales. Elemental analysis estimates suggest loadings range from 5 wt% to 25 wt%. However, due to the limited number of samples, the detailed distribution of the zeolite loading cannot be determined.

[0261] In this example, a 0.3m x 0.9m sample was taken from the roll and selectively colored by immersing it in 1000ml of a 2mol copper sulfate aqueous solution with a pH of 4.8 for 30 minutes. After immersion, the sample was washed twice with deionized water and air-dried. Figure 15 , the material changes from white to light green, and you can see that the color is uneven in different parts (see Figure 15 a).

[0262] Enhanced color development: After the material is dried, place it in a sealed container and fumigate it with 1% hydrogen sulfide gas for 20 minutes. Figure 15 , the distribution of zeolite in a large area can be clearly observed, confirming that the zeolite is unevenly distributed (see Figure 15 b) The presence of a higher loading in areas displaying darker colors and a lower loading in lighter areas confirms that the overall distribution of the zeolite on the gauze carrier can be clearly observed using selective coloration with colorable metal cations and color enhancement treatment. This indicates that the material is uniform on a large scale (0.5 m x 0.5 m), but not uniformly distributed on centimeter and millimeter scales. This rapid acquisition of uniformity information at different scales is not achievable with existing technologies.

[0263] Example 14

[0264] The difference between Example 14 and Example 1 is that:

[0265] In the present embodiment, the material is three zeolite gauze samples provided by Hangzhou Feixin Innovation Material Technology Co., Ltd. The carrier of the sample is all absorbent cotton gauze material, and the zeolite material of the load is chabazite. The original sample carrier material and the loaded zeolite are all white. It is impossible to directly assess the uniformity of the load capacity and load. The three samples are tested using a muffle furnace roasting weight method, and the average zeolite load of the resulting materials is respectively (A) 30wt%, (B) 12wt% and (C) 13wt%.

[0266] Three samples were selectively colored simultaneously in parallel: 30 g of gauze was immersed in a 1 mol / L copper chloride solution (pH 5.2) acidified with hydrochloric acid for copper ion selective coloring. The total mass of the gauze was 500 g of the copper chloride solution. After soaking for 3 minutes, the gauze was washed twice with deionized water and wrung out. Three samples were also enhanced by fumigating them with concentrated ammonia for 10 minutes in a container and then air-drying them for 5 minutes to evaporate excess ammonia.

[0267] Photos of samples at various stages are shown below. Figure 16 As shown:

[0268] Figure 16 (a) is a photograph of sample (A) after selective copper ion coloring, showing the blue-green color of copper ions. The photo shows a uniform color distribution, indicating a high uniformity of zeolite loading.

[0269] Figure 16 b is a photograph of sample (A) after further ammonia fumigation to enhance color development. The purple color comes from the cuprammonium complex ion. The darker color in the photograph indicates a higher loading, and the more uniform the color distribution, the more uniform the zeolite loading.

[0270] Figure 16Figure c and Figure d are photos of samples (B) and (C) after copper ion coloring and ammonia fumigation treatment respectively. Figure 16 b is light, which is consistent with the result that the loading of both samples is less than half of that of sample (A). The darker the color, the higher the loading. Figure 16 b and c have uniform colors, indicating that the zeolite loading is highly uniform.

[0271] Figure 16 d It can be clearly seen that the color distribution in different areas is uneven, and there are some dark spots, indicating that the zeolite loading uniformity is very poor. Figure 16 Two 2mm×2mm micro-area samples were cut from the dark spot area and the light area in d. Thermogravimetric analysis (TGA) showed that the loading capacity of the dark spot area was 24wt%, while the loading capacity of the light area was only 7.5wt%.

[0272] The above experimental results demonstrate that the method of this application can be used to quickly determine the uniformity of the loading distribution of the resulting material. By specifically testing the darkest and lightest areas, upper and lower limits for micro-area loading can be determined with minimal testing. The presence of visible color differences between different areas of the treated sample can be used as a load uniformity indicator for product factory inspection or internal control.

[0273] Example 15

[0274] The difference between Example 15 and Example 1 is that:

[0275] In this example, zeolite with different loadings was loaded onto a cordierite porous ceramic substrate by coating. First, seven standard samples with known loadings were prepared, with loadings of 0.0, 0.2, 0.5, 1.0, 2.0, 5.0, and 10.0 mg / cm 2 .

[0276] Selective Coloring: All ceramic panels were simultaneously immersed in 5 L of a 2 M copper sulfate solution for copper ion exchange coloring. The pH of the solution was adjusted to 5.0. After the ion exchange coloring, the material was rinsed with deionized water for 30 seconds and drained.

[0277] Enhanced color development treatment: In a sealed container, all ceramic plates that have undergone the above selective coloring treatment are clamped with clips and hung above 100 ml of concentrated ammonia water for fumigation for 20 minutes, and then taken out.

[0278] The reflectance spectrum of the test material in the range of 400-750nm is calculated, the average reflectance in this wavelength range is calculated, and the average reflectance is plotted against the loading amount, as shown in the figure. Figure 17 shown.

[0279] See also Figure 17 , it can be seen that when the loading is less than 2.0 mg / cm 2 When the loading amount is more than 3 mg / cm, the average reflectivity shows a good linear relationship with the loading amount. The higher the loading amount, the lower the average reflectivity. However, when the loading amount exceeds 3 mg / cm 2 The average reflectivity has become stable.

[0280] Select 0-2mg / cm 2 The points in the interval are linearly fitted as the working curve. Three more samples are prepared and tested as unknown samples. First, the ion exchange and ammonia fumigation operations are performed using the same method and process. Then the reflectance spectrum is tested and the average reflectance is calculated. Then the corresponding load is calculated according to the working curve and compared with the actual load. The results are also marked on Figure 17 , it can be seen that when the actual loading is 0.25, 0.75 and 1.50 mg / cm 2 The results obtained by this method were 0.27, 0.71 and 1.42 mg / cm 2 .

[0281] The above experimental results indicate that the method of the technical solution proposed in the present invention can be used to quantitatively detect the zeolite loading amount of a planar supported zeolite composite material.

[0282] Example 16

[0283] The difference between Example 16 and Example 1 is that:

[0284] In this embodiment, it is necessary to quickly monitor and analyze the uniformity of products on three parallel production lines.

[0285] The product is absorbent cotton gauze coated with chabazite. On three production lines, a sample of 30 cm wide and 40 cm long was cut with scissors. The three gauze samples removed were all white, and no information on the load and uniformity could be determined (see Figure 18 ), and then selectively coloring: soak the three samples together in a pre-prepared 1000 ml copper sulfate aqueous solution with a concentration of 2 mol per liter, shake for 30 seconds, take out and wring out, put them into a pre-connected 5000 ml tap water, rinse for 20 seconds, and wring out; enhance color development treatment: after loosening the gauze, put it into a transparent fumigation container with concentrated ammonia water pre-placed at the bottom. After about 30 seconds, the gauze will turn blue-purple as a whole; take it out after 60 seconds, spread it flat, and observe and evaluate the uniformity.

[0286] The total time for testing the three samples does not exceed 3 minutes, and the results are shown in Figure 18 ,Depend on Figure 18As can be seen from the results, the first and second lines had uniform zeolite coating, while the third line had significantly uneven coating. This test result allowed us to adjust the equipment's operating conditions to achieve uniform production of zeolite gauze.

[0287] This example demonstrates that the method provided herein can be used to rapidly process multiple samples in parallel during production, completing rapid load uniformity assessment of multiple samples in a very short time for production quality control. Currently, no existing method can achieve such rapid and comprehensive load uniformity assessment of sampled samples.

[0288] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A method for rapidly detecting and evaluating zeolite loading and zeolite loading uniformity in a zeolite composite material, characterized by: The following steps are involved: Step (1), selective coloring: using a colorable metal cation solution to selectively color the zeolite component in the zeolite composite material to be detected; Step (2), color enhancement: using an enhanced color developer to perform an enhanced color development treatment on the zeolite composite material obtained after the selective coloring operation in step (1); Step (3), Detection and evaluation of zeolite loading and loading uniformity: Quantitative detection and evaluation of zeolite loading: prepare 2-20 zeolite composite materials of the same type with known loading as standard samples. The processing of the standard samples is the same as steps (1) and (2). Use optical instruments to test the optical performance parameters of the standard samples, establish the relationship between zeolite loading and optical performance parameters, and obtain a working curve for quantitative testing of loading; By performing the same optical performance parameter test on the zeolite composite material to be tested obtained through the same steps (1) and (2), the zeolite loading amount in the zeolite composite material to be tested is evaluated based on the obtained results and the working curve; The optical performance parameters include absorbance, absorptivity, reflectivity, whiteness, and grayscale value; Detection and evaluation of zeolite loading uniformity, by analyzing the color depth difference at different positions of the zeolite composite material obtained in step (2) to detect and evaluate the zeolite loading uniformity within the sampling area; The color depth difference analysis includes: (a) Qualitative judgment is made by directly observing the color depth of different areas of the sample with the human eye; (b) using an optical instrument to test optical performance parameters of different areas of the sample for quantitative detection and analysis; the optical performance parameters include absorbance, absorptivity, reflectivity, whiteness, and grayscale value; The selective coloring operation in step (1) is specifically as follows: immersing the zeolite composite material in a solution of colorable metal cations, partially replacing the original cations in the zeolite pores with colorable metal cations through an ion exchange reaction, during which the non-zeolite components do not undergo significant ion exchange chemical reactions with the colorable metal cations, ensuring that the colorable metal cations only selectively enter the zeolite component; The enhanced color development treatment in step (2) is specifically as follows: the colorable metal cations introduced into the zeolite composite material after the selective coloring operation in step (1) are chemically reacted with the enhanced color developer molecules, and an in-situ reaction is performed at the location of the colorable metal cations to generate a substance with a darker color than the colorable metal cations.

2. The method for rapid detection and evaluation of zeolite loading and zeolite loading uniformity in a zeolite composite material according to claim 1, characterized in that: The optical instrument includes an absorption spectrum tester, a reflection spectrum tester, a whiteness meter, a camera with a computer, and a color processing system. The optical performance parameters measured by the absorption spectrum tester are absorbance and absorptivity; the optical performance parameter measured by the reflection spectrum tester is reflectivity; the optical performance parameter measured by the whiteness meter is whiteness; the optical performance parameter measured by the camera with a computer is grayscale; and the optical performance parameter measured by the color processing system is grayscale value.

3. The method for rapid detection and evaluation of zeolite loading and zeolite loading uniformity in a zeolite composite material according to claim 1, characterized in that: The enhanced color development treatment in step (2) is as follows: the sample to be tested, which has been treated in step (1), is placed in an atmosphere containing a gaseous enhanced color developer for fumigation treatment, so that the colorable metal cations introduced into the zeolite composite material in step (1) react chemically with the enhanced color developer to generate a substance with a darker color.

4. The method for rapid detection and evaluation of zeolite loading and zeolite loading uniformity in a zeolite composite material according to claim 1, characterized in that: The colorable metal cation is selected from any one of copper ion, iron ion, chromium ion, zinc ion, nickel ion, manganese ion, lead ion, silver ion, cadmium ion, cobalt ion and mercury ion.

5. The method for rapid detection and evaluation of zeolite loading and zeolite loading uniformity in a zeolite composite material according to claim 1, characterized in that: The color enhancing developer is one of ammonia gas, ammonia water, hydrogen sulfide, and alkali metal sulfide solution.

6. The method for rapid detection and evaluation of zeolite loading and zeolite loading uniformity in a zeolite composite material according to claim 5, characterized in that: The alkali metal sulfide solution is one or more combinations of sodium sulfide solution, potassium sulfide solution, ammonium sulfide solution, and lithium sulfide solution.

7. The method for rapid detection and evaluation of zeolite loading and zeolite loading uniformity in a zeolite composite material according to claim 4, characterized in that: When the colorable metal cation is selected from copper ions, the colorable metal cation solution is a copper ion solution, and the pH value of the copper ion solution is below 6.5; When the colorable metal cation is selected from iron ions, the colorable metal cation solution is an iron ion solution, and the pH value of the iron ion solution is below 3.5; When the colorable metal cation is selected from chromium ions, the colorable metal cation solution is a chromium ion solution, and the pH value of the chromium ion solution is below 5.8; When the colorable metal cation is selected from zinc ion, the colorable metal cation solution is a zinc ion solution, and the pH value of the zinc ion solution is below 7.5; When the colorable metal cation is selected from nickel ions, the colorable metal cation solution is a nickel ion solution, and the pH value of the nickel ion solution is below 7.4; When the colorable metal cation is selected from manganese ions, the colorable metal cation solution is a manganese ion solution, and the pH value of the manganese ion solution is below 9.8; When the colorable metal cation is selected from lead ions, the colorable metal cation solution is a lead ion solution, and the pH value of the lead ion solution is below 8.0; When the colorable metal cation is selected from silver ions, the colorable metal cation solution is a silver ion solution, and the pH value of the silver ion solution is below 9.5; When the colorable metal cation is selected from cadmium ions, the colorable metal cation solution is a cadmium ion solution, and the pH value of the cadmium ion solution is below 8.0; When the colorable metal cation is selected from cobalt ions, the colorable metal cation solution is a cobalt ion solution, and the pH value of the cobalt ion solution is below 8.0; Furthermore, the pH value of the colorable metal cation solution is higher than 2.

0.

8. The method for rapid detection and evaluation of zeolite loading and zeolite loading uniformity in a zeolite composite material according to claim 1, characterized in that: The zeolite is selected from one or more combinations of A-type zeolite, X-type zeolite, chabazite, mordenite, faujasite, ZSM-5 zeolite, Y-type zeolite, P-type zeolite, and clinoptilolite; the original cations in the zeolite are one or more combinations of hydrogen ions, lithium ions, sodium ions, potassium ions, calcium ions, magnesium ions, barium ions, and ammonium ions.

9. The method for rapid detection and evaluation of zeolite loading and zeolite loading uniformity in a zeolite composite material according to any one of claims 1 to 8, characterized in that: The zeolite composite material comprises component A and component B, wherein component A is zeolite and component B is non-zeolite.

10. The method for rapid detection and evaluation of zeolite loading and zeolite loading uniformity in a zeolite composite material according to claim 9, characterized in that: The component B is a matrix material or a supporting substance of the matrix material plus other non-zeolite components.

11. The method for rapid detection and evaluation of zeolite loading and zeolite loading uniformity in a zeolite composite material according to claim 10, characterized in that: The matrix material includes textile products made of cotton fibers, textile products made of organic polymer fibers or ceramic matrix material products.

12. The method for rapid detection and evaluation of zeolite loading and zeolite loading uniformity in a zeolite composite material according to claim 11, characterized in that: The textile products made of cotton fibers include gauze, non-woven fabrics, cotton cloth or cotton balls; the textile products made of organic polymer fibers include non-woven fabrics, melt-blown fabrics, gauze or cloth; the materials of the ceramic matrix material products include corundum, cordierite or silicon carbide; the shapes of the ceramic matrix material products include flat plates, cylinders, round tubes, spheres, honeycomb ceramic structures or ceramic fiber braids.

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