CN111781083A - Scale sample analysis method - Google Patents
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Abstract
The invention provides a scale sample analysis method, which comprises the following steps: sequentially carrying out basic firing treatment and acid treatment on the detected scale sample to obtain an acid insoluble substance and a dissolved acid test solution; determining random scale sample components in the detection scale sample; carrying out inductively coupled plasma luminescence spectrum analysis on the dissolved acid test solution to obtain basic analysis data and random analysis data; determining the content of basic scale sample components in the detection scale sample according to the ignition weight loss in the basic ignition treatment, the obtained quality of the acid insoluble substance and the basic analysis data; determining the content of the random scale sample component according to the random analysis data; and carrying out normalization treatment on the content of the basic scale sample component and the content of the random scale sample component to obtain the content of all components of the detection scale sample. The scale sample analysis method provided by the invention can establish a reliable scale analysis system, comprehensively, objectively and systematically analyze all components in the scale sample, shorten the detection period and improve the detection accuracy.
Description
Technical Field
The invention relates to the technical field of scale sample analysis, in particular to a scale sample analysis method.
Background
The phenomena of corrosion, scaling, leakage, dirt blockage and the like of a coal chemical production system often occur, once a fault occurs, great loss of personnel and property can be caused, and the production and long-period stable operation of the device are seriously influenced. The method has the advantages that the dirt is analyzed, the composition of the dirt is known, the corrosion, scaling, leakage, blockage and other tendencies of the coal chemical production system are evaluated, and the dirt blockage symptom is searched, so that the method has very important significance for guaranteeing the safe and stable operation of the production system.
In the prior art, when a scale sample is analyzed, components which possibly exist are generally estimated according to a process theory and actual production experience and the component contents of the components are analyzed one by one, but the components of the scale sample are complex, the content quantification is difficult, the test period is long, the checking amount is large, for the component analysis, a contrast method, an elimination method and a quantitative analysis method are used, the result is reasonably and accurately determined, the operation is complicated, the scale sample composition cannot be comprehensively, objectively and systematically reflected, and the system fault judgment is influenced.
Disclosure of Invention
The invention provides a scale sample analysis method, aiming at the technical problems that the analysis and test period of the scale sample is long, the check amount is large, the operation is complicated, and the composition of the scale sample cannot be comprehensively, objectively and systematically reflected in the prior art.
In order to achieve the above object, the present invention provides a method for analyzing a scale sample, comprising the steps of: sequentially carrying out basic firing treatment and acid treatment on the detected scale sample to obtain an acid insoluble substance and a dissolved acid test solution; determining random scale sample components in the detection scale sample; carrying out inductively coupled plasma luminescence spectrum analysis on the dissolved acid test solution to obtain basic analysis data and random analysis data; determining the content of basic scale sample components in the detection scale sample according to the ignition weight loss in the basic ignition treatment, the obtained quality of the acid insoluble substance and the basic analysis data; determining the content of the random scale sample component according to the random analysis data; and carrying out normalization treatment on the content of the basic scale sample component and the content of the random scale sample component to obtain the content of all components of the detection scale sample.
Further, the scale sample analysis method further comprises: and drying the original scale sample to obtain the detection scale sample.
Further, the basic burning treatment is carried out on the detection scale sample, and the basic burning treatment comprises the following steps: carrying out first burning on the detected scale sample, and determining first weight loss of the first burning; performing second burning on the detected scale sample after the first burning, and determining second weight loss of the second burning, wherein the temperature of the second burning is higher than that of the first burning; determining the content of basic scale sample components in the detection scale sample according to the ignition weight loss in the basic ignition treatment, the obtained quality of the acid insoluble substance and the basic analysis data, wherein the content comprises the following steps: and determining the content of basic scale sample components in the detection scale sample according to the first weight loss, the second weight loss, the mass of the acid insoluble substances and the basic analysis data.
Further, the acid reagent used in the acid treatment process of the detection scale sample at least comprises the following components: hydrochloric acid, nitric acid and perchloric acid.
Further, subjecting the assay soil sample to an acid treatment comprising: sequentially adding hydrochloric acid and nitric acid into the detection scale sample after the second firing to obtain mixed liquid; after the mixed liquid is heated to be clear, adding perchloric acid into the mixed liquid and continuing to heat to be in a smoking state, and adding hydrochloric acid and warm water into the mixed liquid and continuing to heat to be in a boiling state; and filtering the mixed liquid to obtain the acid-insoluble substance and the acid-soluble test solution.
Further, determining the mass of said acid insolubles comprises: carbonizing and ashing the acid-insoluble substance; carrying out acid insoluble substance firing treatment on the acid insoluble substance after carbonization and ashing treatment; and determining the quality of the acid insoluble substance according to the ignition loss in the ignition treatment of the acid insoluble substance.
Further, the determining random scale species in the detection scale sample comprises: and carrying out X-ray fluorescence spectrum analysis on the detected scale sample to determine the random scale sample components.
Further, the X-ray fluorescence spectrum analysis of the detection scale sample comprises: randomly firing the detected scale sample; and carrying out X-ray fluorescence spectrum analysis on the detection scale sample subjected to random burning treatment.
Further, the temperature of the random burning process is equal to the temperature of the second burning.
Further, the step of performing inductively coupled plasma luminescence spectrum analysis on the dissolved acid test solution to obtain random analysis data includes: diluting the dissolved acid test solution under the condition that the detected scale sample is black and the dissolved acid test solution is yellow, and performing inductively coupled plasma luminescence spectrum analysis on the diluted dissolved acid test solution; and under the condition that the acid-dissolving test solution is colorless, directly carrying out inductively coupled plasma luminescence spectrum analysis on the acid-dissolving test solution.
Through the technical scheme provided by the invention, the invention at least has the following technical effects:
the scale sample analysis method comprises the steps of sequentially carrying out basic ignition treatment and acid treatment on a detected scale sample to obtain an acid insoluble substance and an acid-dissolved test solution, weighing ignition weight loss and the mass of the acid insoluble substance in the basic ignition treatment, determining random scale sample components in the detected scale sample, carrying out inductively coupled plasma luminescence spectrum analysis on the acid-dissolved test solution to obtain basic analysis data and random analysis data, determining the content of the basic scale sample components in the detected scale sample according to the ignition weight loss, the mass of the acid insoluble substance and the basic analysis data, determining the content of the random scale sample components according to the random analysis data, and carrying out normalization treatment on the content of the basic scale sample components and the content of the random scale sample components to obtain the content of all components of the detected scale sample. The scale sample analysis method provided by the invention can establish a reliable scale analysis system, comprehensively, objectively and systematically analyze all components in the scale sample, reduce the detection workload, shorten the detection period, improve the detection accuracy, facilitate the search of the fault reasons of the coal chemical production system, reduce the large loss and waste of manpower and material resources during the maintenance of the coal chemical device, and ensure the safe and stable operation of the coal chemical production system.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a flow chart of a method for analyzing a scale sample according to an embodiment of the present invention.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating embodiments of the invention, are given by way of illustration and explanation only, not limitation.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
In the present invention, unless specified to the contrary, use of the terms of orientation such as "upper, lower, top, bottom" or the like are generally described with respect to the orientation shown in the drawings or the positional relationship of the components with respect to each other in the vertical, or gravitational direction.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
Referring to fig. 1, an embodiment of the present invention provides a method for analyzing a scale sample, including the following steps: s101: sequentially carrying out basic firing treatment and acid treatment on the detected scale sample to obtain an acid insoluble substance and a dissolved acid test solution; s102: determining random scale sample components in the detection scale sample; s103: carrying out inductively coupled plasma luminescence spectrum analysis on the dissolved acid test solution to obtain basic analysis data and random analysis data; s104: determining the content of basic scale sample components in the detection scale sample according to the ignition weight loss in the basic ignition treatment, the obtained quality of the acid insoluble substance and the basic analysis data; s105: determining the content of the random scale sample component according to the random analysis data; s106: and carrying out normalization treatment on the content of the basic scale sample component and the content of the random scale sample component to obtain the content of all components of the detection scale sample.
Specifically, in the embodiment of the invention, basic scale sample components in the scale sample are judged by combining the appearance and the working condition of the scale sample, wherein the basic scale sample components comprise organic matters, sulfides, acid insoluble substances, carbonates, iron, aluminum, calcium, magnesium and phosphorus. And then manufacturing a detection scale sample, sequentially carrying out basic burning treatment and acid treatment on the detection scale sample to obtain an acid insoluble substance and a dissolved acid test solution, weighing the mass of the detection scale sample after each basic burning treatment, and determining the burning weight loss in each basic burning treatment. And then determining random scale sample components in the detected scale sample, and performing inductively coupled plasma luminescence spectrum analysis on the dissolved acid test solution according to the basic scale sample components and the random scale sample components to obtain basic analysis data and random analysis data.
Organic matters, sulfides and carbonates in the detection scale sample are removed during the burning treatment, and acid insoluble substances are calculated by silicon dioxide, so that the content of the organic matters, the sulfides and the carbonates in the detection scale sample can be determined according to the burning weight loss in the basic burning treatment, the content of the silicon dioxide can be determined according to the quality of the acid insoluble substances, and then the content of the residual basic scale sample components in the detection scale sample is determined according to basic analysis data. Because the components of the random scale sample cannot be judged in advance according to the appearance and the working condition of the scale sample, the components of the random scale sample need to be determined by an analysis means, and then the content of the components of the random scale sample is determined by carrying out inductively coupled plasma luminescence spectrum analysis on the dissolved acid test solution. And then, calculating and returning the sum of the measured content of the basic scale sample components and the content of the random scale sample components to 100 percent to obtain the content of all components of the detected scale sample. For example, when the percentage content of the alumina in the scale sample is detected to be 16.49%, the total content is 100.54%, and the percentage content is normalized to be 100%, the content of the alumina is 16.49 × 100/100.54% -16.40%.
After the content of all the components of the detected scale sample is judged, the coal chemical production system can be monitored according to the scale sample analysis result and the scale sample appearance and by combining working conditions, the corrosion, scaling, leakage, blockage or microorganism hazard conditions of the production operation system and the like can be judged, and the obstacles of the coal chemical production system can be diagnosed.
According to the scale sample analysis method provided by the invention, a reliable scale analysis system can be established, all components in the scale sample can be comprehensively, objectively and systematically analyzed, the detection workload is reduced, the detection period is shortened, the detection accuracy is improved, the fault reason of the coal chemical production system is conveniently found, a large amount of loss and waste of manpower and material resources during maintenance of the coal chemical device are reduced, and the safe and stable operation of the coal chemical production system is ensured.
Further, the scale sample analysis method further comprises: and drying the original scale sample to obtain the detection scale sample.
Specifically, in the present embodiment, a certain amount of original scale sample is collected, transferred into a ceramic evaporation dish, and dried at 105 ℃. + -. 5 ℃ for 2-8 hours (the time period depends on the water content of the original scale sample). After the original scale sample is slightly cooled, the scale sample is fully ground in a mortar, sieved by a sieve with 80-120 meshes and dried at 105 +/-5 ℃ to constant weight to be used as a scale sample for detection.
According to the scale sample detection method provided by the invention, the original scale sample is pretreated, so that the influence of water in the original scale sample is removed, the accuracy of scale sample analysis is improved, and meanwhile, the original scale sample is processed into powder, so that the weighing and further detection in the next analysis process can be facilitated.
Further, the basic burning treatment is carried out on the detection scale sample, and the basic burning treatment comprises the following steps: carrying out first burning on the detected scale sample, and determining first weight loss of the first burning; performing second burning on the detected scale sample after the first burning, and determining second weight loss of the second burning, wherein the temperature of the second burning is higher than that of the first burning; determining the content of basic scale sample components in the detection scale sample according to the ignition weight loss in the basic ignition treatment, the obtained quality of the acid insoluble substance and the basic analysis data, wherein the content comprises the following steps: and determining the content of basic scale sample components in the detection scale sample according to the first weight loss, the second weight loss, the mass of the acid insoluble substances and the basic analysis data.
Specifically, in the embodiment of the invention, the hollow ceramic crucible is burned to constant weight at 950 ℃ in advance, a certain amount of detection scale sample is weighed, the crucible is moved into the hollow ceramic crucible, the crucible is moved into a muffle furnace to be burned to constant weight at 550 +/-5 ℃, the mass of the crucible is weighed after the temperature is reduced to room temperature, and the first weight loss of the first burning is determined. And then, continuously moving the crucible after the first ignition into a muffle furnace, igniting to constant weight at 950 +/-10 ℃, weighing the mass of the crucible after the temperature is reduced to room temperature, and determining the second weight loss of the second ignition.
After the basic analysis data are determined, determining the content of basic scale sample components in the detected scale sample according to the first weight loss, the second weight loss, the mass of the acid insoluble substances and the basic analysis data. Removing organic matters and sulfides in the detection scale sample in the first burning process, determining whether the organic matters or the sulfides are in the detection scale sample by combining the working condition and the appearance of the detection scale sample, and determining the content of the organic matters or the sulfides in the detection scale sample according to the first weight reduction; and removing the carbonate in the scale sample during the second burning, so that the content of the carbonate in the detected scale sample can be determined according to the second weight reduction.
Further, the acid reagent used in the acid treatment process of the detection scale sample at least comprises the following components: hydrochloric acid, nitric acid and perchloric acid.
Specifically, in the embodiment of the present invention, the acid reagents used in the acid treatment process are respectively: concentrated hydrochloric acid with the density of rho (HCl) 1.19g/mL) and the grade of superior purity; concentrated nitric acid, density rho (HNO)3) 1.19g/mL), grade is guaranteed to be superior pure; perchloric acid, density is rho (HClO)4) 1.76g/mL) and grade no.
Further, subjecting the assay soil sample to an acid treatment comprising: sequentially adding hydrochloric acid and nitric acid into the detection scale sample after the second firing to obtain mixed liquid; after the mixed liquid is heated to be clear, adding perchloric acid into the mixed liquid and continuing to heat to be in a smoking state, and adding hydrochloric acid and warm water into the mixed liquid and continuing to heat to be in a boiling state; and filtering the mixed liquid to obtain the acid-insoluble substance and the acid-soluble test solution.
Specifically, in the embodiment of the invention, the detection scale sample after the second burning is moved into a 250mL beaker, a small amount of water is added to be mixed into paste, and hydrochloric acid and nitric acid are sequentially added to obtain the mixed liquid. After the mixed liquid is heated to be clear, perchloric acid is added into the mixed liquid and the mixed liquid is continuously heated to be in a smoking state, and hydrochloric acid and warm water are added into the mixed liquid and the mixed liquid is continuously heated to be in a boiling state. Filtering the acid insoluble substance with quantitative filter paper, collecting the filtrate in a volumetric flask, cooling, and diluting with water to a scale to obtain the acid-soluble test solution.
Further, determining the mass of said acid insolubles comprises: carbonizing and ashing the acid-insoluble substance; carrying out acid insoluble substance firing treatment on the acid insoluble substance after carbonization and ashing treatment; and determining the quality of the acid insoluble substance according to the ignition loss in the ignition treatment of the acid insoluble substance.
Specifically, in the embodiment of the invention, after filtering the acid-insoluble substances, the filter paper wrapping the acid-insoluble substances is moved into an air porcelain crucible which is burnt at 950 ℃ in advance to have constant weight, and carbonization and low-fire ashing treatment are carried out on an electric heating furnace, so that impurities such as hydrogen, oxygen, carbon and the like in the filter paper and the acid-insoluble substances are removed, and incombustible silicon dioxide in the acid-insoluble substances is retained. Then transferring the acid insoluble substance into a muffle furnace, burning the acid insoluble substance to constant weight at 950 +/-10 ℃, and determining the quality of the acid insoluble substance according to the burning weight loss in the burning treatment of the acid insoluble substance.
According to the scale sample detection method provided by the invention, impurities in the acid insoluble substances can be removed, the quality of the acid insoluble substances can be accurately weighed, the direct combustion of the acid insoluble substances in the muffle furnace during firing is avoided, the component loss is avoided, and the detection accuracy is improved.
Further, the determining random scale species in the detection scale sample comprises: and carrying out X-ray fluorescence spectrum analysis on the detected scale sample to determine the random scale sample components.
Further, the X-ray fluorescence spectrum analysis of the detection scale sample comprises: randomly firing the detected scale sample; and carrying out X-ray fluorescence spectrum analysis on the detection scale sample subjected to random burning treatment.
Further, the temperature of the random burning process is equal to the temperature of the second burning.
Specifically, in the embodiment of the invention, 10-20g of the pretreated detection scale sample is weighed, is placed in an empty porcelain crucible which is burnt at 950 ℃ in advance to have constant weight, is moved into a muffle furnace to be burnt at 950 +/-10 ℃ to remove organic matters, sulfate and carbonate in the detection scale sample, is cooled and weighed, and the requirement of X-ray fluorescence spectrum analysis can be met by ensuring that the mass of the detection scale sample is not less than 3 g. The real content ratio of the components with the X-ray fluorescence spectrum analysis result of less than 1000ppm in the detection scale sample is extremely small, and the system obstacle diagnosis can not be influenced, so that the components can be ignored.
Further, the step of performing inductively coupled plasma luminescence spectrum analysis on the dissolved acid test solution to obtain random analysis data includes: diluting the dissolved acid test solution under the condition that the detected scale sample is black and the dissolved acid test solution is yellow, and performing inductively coupled plasma luminescence spectrum analysis on the diluted dissolved acid test solution; and under the condition that the acid-dissolving test solution is colorless, directly carrying out inductively coupled plasma luminescence spectrum analysis on the acid-dissolving test solution.
Specifically, in the embodiment of the present invention, the dissolved acid solution needs to be diluted correspondingly according to the appearance of the scale sample and the dissolved acid solution, so as to avoid the detection result exceeding the standard curve range or exceeding the strength range detected by the instrument. Diluting the dissolved acid test solution under the condition that the detected scale sample is black and the dissolved acid test solution is yellow, carrying out inductively coupled plasma luminescence spectrum analysis on the diluted dissolved acid test solution, and directly carrying out inductively coupled plasma luminescence spectrum analysis on the dissolved acid test solution under the condition that the dissolved acid test solution is colorless.
Example one
And (3) judging basic scale sample components in the scale sample by combining the appearance and the working condition of the original scale sample, wherein the basic scale sample components comprise organic matters, sulfides, acid insoluble substances, carbonate, iron, aluminum, calcium, magnesium and phosphorus. A certain amount of representative and uniform original scale sample is collected, transferred into a porcelain evaporation dish and dried for more than 2-8 hours at 105 +/-5 ℃ (the time is determined according to the water content of the original scale sample). And (3) after the scale sample is slightly cooled, fully grinding the scale sample in a mortar, sieving the scale sample by adopting a 80-120-mesh sieve, and drying the scale sample at 105 +/-5 ℃ to constant weight to obtain the scale sample for detection.
Weighing 0.5 +/-0.0002 g of detected scale sample, moving the detected scale sample into an empty porcelain crucible which is burnt at 950 ℃ to constant weight in advance, weighing the mass of an initial crucible, moving the crucible into a muffle furnace to be burnt at 550 +/-5 ℃ to constant weight, weighing the mass of the crucible which is burnt at 550 +/-5 ℃, and determining the first weight loss according to the difference value of the mass of the initial crucible and the mass of the initial crucible. And (3) continuously moving the crucible burnt to constant weight at 550 +/-5 ℃ into a muffle furnace, burning to constant weight at 950 +/-10 ℃, weighing the mass of the crucible burnt at 950 +/-5 ℃, and determining the second weight loss according to the difference value of the mass of the crucible before the second burning.
Transferring the detection scale sample after burning at 950 ℃ to a 250mL beaker, adding a small amount of water to prepare paste, slowly adding 30mL of hydrochloric acid (hydrochloric acid can be added in batches for the detection scale sample with more carbonate) and 10mL of nitric acid, covering a watch glass, and shaking uniformly to obtain a mixed liquid. Slowly heating the mixed liquid on an electric heating furnace until the mixed liquid is boiled, and keeping for 20min until the mixed liquid is clear. Taking down the beaker, adding 20mL perchloric acid after cooling slightly, heating slowly until smoking, keeping for 15-20min, taking down the beaker from an electric heating furnace, adding 10mL hydrochloric acid and 50mL warm water after cooling, boiling, filtering with medium-speed quantitative filter paper while hot after fully stirring, washing with 1% nitric acid solution, and washing with hot water until the filtrate does not contain chloride ions (checking with silver nitrate) to obtain acid insoluble substances. Collecting the filtrate and the washing solution in a 250mL volumetric flask, cooling, diluting to the scale with water, and shaking up to obtain the acid-dissolved test solution.
Transferring the filter paper wrapped with the acid insoluble substance into an air porcelain crucible which is burned at 950 ℃ in advance to have constant weight, performing carbonization and small fire ashing treatment on the filter paper and the acid insoluble substance on an electric heating furnace, removing impurities such as hydrogen, oxygen, carbon and the like in the filter paper and the acid insoluble substance, and retaining incombustible silicon dioxide in the acid insoluble substance. Then the mixture is moved into a muffle furnace to be burned to constant weight at 950 +/-10 ℃, and the quality of the acid insoluble substance is determined according to the quality difference of the crucible before and after the acid insoluble substance is burned.
Weighing 10-20g of the pretreated detection scale sample into an empty porcelain crucible which is burned at 950 ℃ in advance to have constant weight, transferring the crucible into a muffle furnace to be burned at 950 +/-10 ℃, cooling, accurately weighing 3g of the burned detection scale sample, accurately weighing the sample to 0.01g, and placing the sample in a sample cup. Then, X-ray fluorescence spectrum analysis is carried out to determine the components of the random scale sample, and the components with the X-ray fluorescence spectrum analysis result less than 1000ppm are ignored.
Then, carrying out inductively coupled plasma luminescence spectrum analysis on the dissolved acid test solution:
1) and (3) drawing a calibration curve: and respectively transferring a certain volume of multi-component mixed standard solution (BWB2389-2016), and sequentially preparing a series of standard solutions of the elements to be detected by adopting 1% nitric acid solution, wherein the concentrations of the standard solutions are respectively 0, 10, 20, 40, 80 and 100 ug/ml. And (3) introducing the standard solution into an inductively coupled plasma luminescence spectrum analyzer from low concentration to high concentration in sequence, measuring the emission intensity according to the reference measurement condition of the analyzer, and establishing a calibration curve of the target element by taking the mass concentration (ug/ml) of the target element series as a horizontal coordinate and the emission intensity value as a vertical coordinate.
2) Measurement of the sample: the system was flushed with 1% nitric acid solution until the blank intensity value decreased to the minimum, and after the analytical signal stabilized, the sample was analyzed under the same conditions as the calibration curve was established.
3) Determination of blank sample: the blank sample was measured according to the same procedure as the sample measurement.
4) According to the appearance color of the dirty sample and the color of the acid-dissolving test solution, the acid-dissolving test solution is diluted by pure water in a proper proportion. If the detected scale sample is black and the acid-dissolving test solution is yellow, diluting the acid-dissolving test solution by 5-20 times, and performing inductively coupled plasma luminescence spectrum analysis on the diluted acid-dissolving test solution; if the acid-soluble sample solution is colorless, it is directly analyzed without dilution. Inputting the residual basic scale sample components, random scale sample components, dilution times, detection scale sample mass of 0.5g and dissolved acid test solution volume of 250mL into analysis software of the inductively coupled plasma luminescence spectrum analyzer, and directly reading the content of the residual basic scale sample components and the content of the random scale sample components in the detection scale sample.
And then, calculating and returning the sum of the measured content of the basic scale sample components and the content of the random scale sample components to 100 percent to obtain the content of all components of the detected scale sample. For example, when the percentage content of the alumina in the scale sample is detected to be 16.49%, the total content is 100.54%, and the percentage content is normalized to be 100%, the content of the alumina is 16.49 × 100/100.54% -16.40%.
After judging the content of all components of the detected scale sample, monitoring the coal chemical production system by combining working conditions, scale sample analysis results and scale sample appearance, judging the corrosion, scaling, leakage, blockage or microorganism hazard conditions of the production operation system and the like, diagnosing the obstacles of the coal chemical production system, and rectifying:
example two
Analyzing the components of dirt on the shell (inlet) of the water washing heat exchanger: the original dirty appearance was grey brown, muddy, oily and oily. The results of X-ray fluorescence spectrum analysis are shown in Table 1, and the results of scale sample analysis are shown in Table 2.
| Serial number | Molecular formula | Content (wt.) | Remarks for note |
| 1 | AL2O3 | 53.20％ | |
| 2 | Cr2O3 | 16.30％ | |
| 3 | P2O5 | 12.50％ | |
| 4 | Si02 | 11.70％ | |
| 5 | Fe2O3 | 2.51％ | |
| 6 | CaO | 1.79％ | |
| 7 | MgO | 1.70％ | |
| 8 | ZnO | 0.17％ | |
| 9 | CuO | 0.08％ | |
| 10 | TiO2 | 943ppm | Can be ignored |
| 11 | K2O | 553ppm | Can be ignored |
| 12 | SrO | 241ppm | Can be ignored |
| 13 | ZrO2 | 228ppm | Can be ignored |
TABLE 1X-ray fluorescence Spectroscopy results
TABLE 2 results of scale analysis
1. Diagnosis of cause:
1) the original dirty appearance was grey brown, muddy, oily. The contents of organic substances (with oil stain and oil smell), silicon and aluminum (gray and muddy) in the dirt are higher, and the content of iron (brown) is lower.
2) The on-site working condition is a Methanol To Olefin (MTO) device. From the results of scale analysis, it can be seen that the basic scale components of the scale mainly include 550 ℃ ignition weight loss, 950 ℃ ignition weight loss, acid insoluble substances, ferric oxide, aluminum oxide, calcium oxide, magnesium oxide, and phosphorus pentoxide, and the random scale components mainly include chromium oxide, zinc oxide, and copper oxide. Wherein the ignition weight loss (organic matter) at 550 ℃ is 65.71 percent, the acid insoluble matter (silicon dioxide) and aluminum content is high, and the chromium, calcium, magnesium, iron, zinc, copper, phosphorus and carbonate content is low.
3) The main raw material of the MTO device is methanol, and the reaction mechanism is that the methanol is converted into hydrocarbons under the action of an acidic molecular sieve catalyst special for MTO. The device comprises a reaction regeneration system, a quench water washing and sewage stripping system (quench stripping system for short) and a heat recovery system. The water washing heat exchanger of the embodiment belongs to a quenching stripping system. The water washing water heat exchanger comprises a quench tower, a water washing tower and a sewage stripping tower. The process is that reaction gas from a reaction system is passed through a quench tower and a water scrubber to remove overheat and wash catalyst, most of water is condensed and then sent to a downstream olefin separation device (LORU) for separating and refining ethylene and propylene, and water condensed in the quench water scrubber is passed through a sewage stripping tower to recover a small amount of organic matters such as methanol, dimethyl ether and the like for recycling.
4) The acidic molecular sieve catalyst special for MTO is a metal modified catalyst taking SAPO-34 molecular sieve as a framework, the components of the molecular sieve framework mainly contain aluminum, phosphorus and silicon, and the added modified metals mainly comprise copper, zinc, calcium, magnesium, iron, chromium, strontium and the like, and are consistent with the analysis result of X-ray fluorescence spectrum. The washing water heat exchanger is made of carbon steel and iron-carbon alloy, and the scale removing layer does not show that the tube wall of the heat exchanger tube bundle is corroded. And (3) judging that the acid insoluble substances mainly come from catalyst powder, the organic substances mainly come from hydrocarbons, methanol, dimethyl ether and the like, and the hydrocarbons belong to petroleum by combining an on-site process, a scale sample analysis result and the appearance of the scale sample, so that the water washing heat exchanger is diagnosed to be in a scale formation state, and the scale is mainly formed by the organic substances and the catalyst. The tracing reason is that the effect of the solid and oil removing facility of the quenching water washing is poor, and the loss of the catalyst is large and the content of the organic matter is high.
2. The rectification measures are as follows:
1) according to the qualitative diagnosis result, measures are made, timely correction and modification are carried out, and technical modification is carried out on the rapid cooling, oil removal and fixation removal device, so that the catalyst running loss is reduced, the capacity of the heat exchanger is increased, and the high-load operation of the device is ensured.
2) The method provides guidance for performance parameters of the catalyst, and selects the catalyst with high abrasion index to reduce the running loss.
3) And (3) adding an auxiliary agent into the washing water to disperse and strip the mixture, so that the deposition is reduced. 5kg/h of RdSaien water dispersant is added to achieve the cleaning effect. The cleaning cycle of the water-washing heat exchanger before the rectification is once every two weeks, and the cleaning cycle of the water-washing heat exchanger after the rectification is once every four months. The labor cost and the cleaning and installing cost are greatly saved, the production and operation efficiency is improved, and the production and operation cost is reduced.
4) Since the alkali metal is inevitably contained in the purchased methanol, the acidity or even the structure of the MTO catalyst is changed during a long-term operation, resulting in a decrease in the main reaction ability and an increase in side reactions, and such a change is irreversible and non-reproducible. Therefore, the lower the content of alkali metal in the raw material methanol is, the better the content is, side reaction is limited, the reaction capability is improved, the long-term stability of the catalyst is ensured, the catalyst is prevented from fast falling off and entering water washing water to form deposition, and the efficiency of the heat exchanger is reduced.
EXAMPLE III
Analyzing the blockage of an inlet regulating valve of a liquid ammonia evaporator of a desulfurization and denitrification unit: the appearance of the dirt sample is white powder, has irritant ammonia smell, is oil stain, is gradually brown in color in the air, and becomes black after being burned. The results of X-ray fluorescence spectrum analysis are shown in Table 3, and the results of scale sample analysis are shown in Table 4.
| Serial number | Molecular formula | Content (wt.) | Remarks for note |
| 1 | Fe2O3 | 93.29％ | |
| 2 | Si02 | 3.98％ | |
| 3 | AL2O3 | 1.76％ | |
| 4 | CaO | 0.27％ | |
| 5 | MgO | 0.14％ | |
| 6 | K2O | 0.05％ | |
| 7 | Na2O | 976ppm | Can be ignored |
| 8 | CuO | 823ppm | Can be ignored |
| 9 | Cl | 821ppm | Can be ignored |
| 10 | ZnO | 751ppm | Can be ignored |
| 11 | P2O5 | 658ppm | Can be ignored |
| 12 | Cr2O3 | 297ppm | Can be ignored |
| 13 | TiO2 | 284ppm | Can be ignored |
| 14 | BaO | 273ppm | Can be ignored |
| 15 | Ce2O3 | 92.3ppm | Can be ignored |
| 16 | SrO | 74.0ppm | Can be ignored |
| 17 | As2O3 | 72.6ppm | Can be ignored |
| 18 | ZrO2 | 25.0ppm | Can be ignored |
TABLE 3X-ray fluorescence Spectroscopy results
TABLE 4 results of analysis of scale
1. Diagnosis of cause:
1) the sample was seen as a white powder outside the original scale, with oil stains, gradually changing brown in color in air, and becoming black after ignition, indicating that there was much iron (blackened after ignition) and organic matter (with oil stains).
2) The site working condition is ammonia desulfurization and denitrification. From the results of the scale analysis, it can be seen that the basic scale components of the scale mainly include 550 ℃ ignition weight loss, 950 ℃ ignition weight loss, acid insoluble substances, ferric oxide, aluminum oxide, calcium oxide, magnesium oxide, and the random scale components mainly include potassium oxide. Wherein the weight loss (organic matter) is reduced by burning at 550 ℃, the content of acid insoluble substances (silicon dioxide), iron and aluminum is larger, and the content of calcium, magnesium and potassium is smaller.
3) In the scale sample analysis result, the iron content is 62.08 percent, the proportion is large, and the organic matter content is 26.79 percent, the proportion is large. The desulfurization and denitrification unit system does not produce oil stains on site, the pipe wall is not corroded after the blockage is stripped, the synthetic ammonia production process determines that liquid ammonia manufacturers inevitably have liquid ammonia residues, and the higher the residue content is, the lower the liquid ammonia grade rate is. These liquid ammonia residues include: catalyst powder (containing iron, aluminum, potassium and the like) of synthetic ammonia and wrapped oil stain. The iron and organic matters in the scale sample are mainly from liquid ammonia.
4) The method is characterized in that the working condition, the scale sample analysis result and the scale sample appearance are combined, the blockage of the liquid ammonia valve is diagnosed to be residue in purchased liquid ammonia, ammonia scale is formed, namely, a catalyst in synthetic ammonia production is aged and then falls off, impurities such as compressor oil, catalyst powder, rust and the like are suspended in the liquid ammonia, the impurities and the liquid ammonia enter an evaporator coil, and the residue is separated out after the liquid ammonia is gasified, so that the valve is blocked.
2. The rectification measures are as follows:
after an inlet adjusting valve of a liquid ammonia evaporator of the denitration unit is blocked, the exhaust smoke pollutants of the boiler can exceed the standard, an environmental protection event is caused, and the boiler is stopped when the exhaust smoke pollutants are serious. The liquid ammonia valve belongs to the explosion-proof type, and is not suitable for frequently decomposing to remove ammonia scale, and the valve can be damaged due to frequent decomposition of the valve, so that under the condition that the blockage is determined to be liquid ammonia residue, the liquid ammonia storage tank is emptied and then is purged by using nitrogen, and then new liquid ammonia is used, so that the pipeline and the valve are prevented from being blocked due to excessive residue of the liquid ammonia residue; or the liquid ammonia product with high outsourcing grade rate and low oil content reduces pollution and blockage, and simultaneously can also reduce a large amount of loss and waste of manpower and material resources during maintenance of the coal chemical device.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A method for analyzing a scale sample, comprising the steps of:
sequentially carrying out basic firing treatment and acid treatment on the detected scale sample to obtain an acid insoluble substance and a dissolved acid test solution;
determining random scale sample components in the detection scale sample;
carrying out inductively coupled plasma luminescence spectrum analysis on the dissolved acid test solution to obtain basic analysis data and random analysis data;
determining the content of basic scale sample components in the detection scale sample according to the ignition weight loss in the basic ignition treatment, the obtained quality of the acid insoluble substance and the basic analysis data;
determining the content of the random scale sample component according to the random analysis data;
and carrying out normalization treatment on the content of the basic scale sample component and the content of the random scale sample component to obtain the content of all components of the detection scale sample.
2. A scale sample analysis method according to claim 1, further comprising:
and drying the original scale sample to obtain the detection scale sample.
3. A method of analyzing a scale sample according to claim 2, wherein the basic burning treatment of the detection scale sample comprises:
carrying out first burning on the detected scale sample, and determining first weight loss of the first burning;
performing second burning on the detected scale sample after the first burning, and determining second weight loss of the second burning, wherein the temperature of the second burning is higher than that of the first burning;
determining the content of basic scale sample components in the detection scale sample according to the ignition weight loss in the basic ignition treatment, the obtained quality of the acid insoluble substance and the basic analysis data, wherein the content comprises the following steps:
and determining the content of basic scale sample components in the detection scale sample according to the first weight loss, the second weight loss, the mass of the acid insoluble substances and the basic analysis data.
4. A scale sample analysis method according to claim 3, wherein the acid reagent used in the acid treatment of the measurement scale sample comprises at least: hydrochloric acid, nitric acid and perchloric acid.
5. A scale sample analysis method according to claim 4, wherein the detection scale sample is subjected to an acid treatment comprising:
sequentially adding hydrochloric acid and nitric acid into the detection scale sample after the second firing to obtain mixed liquid;
after the mixed liquid is heated to be clear, adding perchloric acid into the mixed liquid and continuing to heat to be in a smoking state, and adding hydrochloric acid and warm water into the mixed liquid and continuing to heat to be in a boiling state;
and filtering the mixed liquid to obtain the acid-insoluble substance and the acid-soluble test solution.
6. A method for assaying scale samples according to claim 5 wherein determining the mass of the acid insoluble material comprises:
carbonizing and ashing the acid-insoluble substance;
carrying out acid insoluble substance firing treatment on the acid insoluble substance after carbonization and ashing treatment;
and determining the quality of the acid insoluble substance according to the ignition loss in the ignition treatment of the acid insoluble substance.
7. A method for analyzing a scale sample according to claim 3, wherein the determining random scale elements in the detected scale sample comprises:
and carrying out X-ray fluorescence spectrum analysis on the detected scale sample to determine the random scale sample components.
8. A method according to claim 7, wherein said X-ray fluorescence spectroscopy of said detected scale sample comprises:
randomly firing the detected scale sample;
and carrying out X-ray fluorescence spectrum analysis on the detection scale sample subjected to random burning treatment.
9. A method for analyzing a scale sample according to claim 8, wherein the temperature of the random burning process is equal to the temperature of the second burning.
10. A method according to claim 1, wherein said inductively coupled plasma emission spectroscopy of said solubilized acid sample to obtain random analytical data comprises:
diluting the dissolved acid test solution under the condition that the detected scale sample is black and the dissolved acid test solution is yellow, and performing inductively coupled plasma luminescence spectrum analysis on the diluted dissolved acid test solution;
and under the condition that the acid-dissolving test solution is colorless, directly carrying out inductively coupled plasma luminescence spectrum analysis on the acid-dissolving test solution.
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