CN101806681B - Optimal digestion method in waste colloidal particle heavy metal measurement - Google Patents
Optimal digestion method in waste colloidal particle heavy metal measurement Download PDFInfo
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- CN101806681B CN101806681B CN2010101336168A CN201010133616A CN101806681B CN 101806681 B CN101806681 B CN 101806681B CN 2010101336168 A CN2010101336168 A CN 2010101336168A CN 201010133616 A CN201010133616 A CN 201010133616A CN 101806681 B CN101806681 B CN 101806681B
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Abstract
The invention relates to an optimal digestion method in waste colloidal particle heavy metal measurement. Conditions such as different digestive juice systems, digestive temperature, digestive time, high-temperature ashing and the like of a waste colloidal particle sample are performed with orthogonal test research; and heavy metal element content in the sample is measured by the ICP-AES method so as to find a feasible digestion method of the waste colloidal particle sample. The experiment result shows that 1 part of HNO3, 1 part of HClO4 and 4 parts of H2SO4 are adopted to digest at the temperature of 190 DEG C for one hour to completely and fully decompose the sample. The method is accurate, sensitive and quick.
Description
Technical field
The invention belongs to environmental protection technical field, relate to reasonable, the safe handling method of scrap rubber grain.The best digestion method in a kind of waste colloidal particle heavy metal measurement of saying so more specifically.
Background technology
Waste old is meant leftover pieces that the various rubbers that are replaced and rubber produce in producing and waste material etc.Wherein major part becomes refuse because of being regarded as " industrial refuse ".Not only contaminated air, and contaminated soil easily leads to serious fire simultaneously.To the processing of these scrap rubbers,, mainly be to bury or stack in early 1990s.Subsequently, because scrap rubber quantity constantly increases, people's environmental protection and resource reutilization consciousness strengthens gradually and buries and reason such as more and more is restricted, the utilization of scrap rubber comes into one's own day by day, now developed into being referred to as of a kind of hot topic " E industry " (being environmental protection industry) because of one speech of environmental protection in the English is a novel industry with letter " E " beginning
Developed country takes much count of the utilization of waste old.Along with the raising of economic development and people's living standard, world's rubber-consumer amount constantly increased, and nineteen ninety-five is 1,552 ten thousand tons, was upgraded to 1,679 ten thousand tons by 1999, reached 1,950 ten thousand tons in 2004.The waste old generation also increases thereupon simultaneously.For reducing environmental pollution, eliminate because of piling up damaged tire and lead to serious disaster hidden-trouble, countries in the world begin to utilize waste rubber resources cultivating novel industry one after another, and provide more job opportunity for society.In order to promote the raising of waste old utilization factor, rubber circle backroom boys and relevant departments thereof classify the waste old utilization one of as popular research topic.
China's waste old generation estimate in recent years approximately to reach 1,500,000 tons, and utilization factor only is about 45%.Because domestic rubber-consumer amount growth is very fast, therefore as not improving the waste old utilization factor as early as possible, our waste old burden will get more and more, and this is the big problem of environmental protection of being badly in need of solution.
Through consulting related data, in recent years, the development of the utilization of China's waste old was very fast, but reclaimed rubber remains the main path that China's scrap rubber material utilizes, and fine glue powder and tire vulcanizing await further developing.
People think a kind of very effective method to reclaimed rubber production over a period to come, so reclaimed rubber production also becomes the main mode that waste old is handled.But because the reclaimed rubber energy consumption is big, the noise that produces in the production, stink and waste water can't effectively solve for a long time to problems such as second environmental pollution, the human requirement that in the modern life, environmental quality is improved and day by day serious environmental pollute the more and more serious contradiction of formation.Add the rapid growth owing to world economy, the rise of scrap rubber price and other related factors cause the superiority of reclaimed rubber constantly to be desalinated, and the with serious pollution negative effect of reclaimed rubber continues to increase.Though China's reclaimed rubber production accounts for the leading position that regenerating waste or used rubber utilizes, the economic benefit situation of whole industry is extremely unreasonable.According to the rule of development of world economy, to the adjustment that the direction and the outlet of China's reclaimed rubber industry development are made essence as early as possible, the production of waste and old colloidal particles and application are one of most promising modes, should strengthen the dynamics of application and development.
At present, China scientific and technical personnel have made outstanding contribution in effective utilization of waste old, as: utilize waste old to lay plastic cement race track, make sound-proof wall, as paveio(u)r or the like.These all are the approach that better fully utilizes, and not only waste old are utilized, but also have played the effect of protecting environment.
At present, the imagination with waste old grain laying lawn also is a kind of effective way of waste old comprehensive utilization.Sports turf is mainly used in the football match, owing to trampled for a long time, influences the growth of turfgrass, is easy to lose original elasticity.In the past, the methods that adopt finishing or heavily litter the level ground more.Though certain effect is arranged, has caused the waste on time and the fund.If adopt and in soil, mix a certain amount of waste old grain, not only can reduce finishing number of times to the lawn, reduce capital consumption, under the prerequisite of the normal growth that does not influence the lawn, keep the elasticity on lawn simultaneously.
Whether at present, owing to principal ingredient in the waste and old colloidal particles is sulfohydrate and some heavy metal elements, it is mixed in the soil can exert an influence to environment, we are also unknown.Therefore, need carry out sample pretreatment to waste old, energy fast measuring wherein contents of heavy metal elements then is a very useful job.
The organic sample pre-service has two kinds of methods, and they are wet method digestion and dry method digestion, and both respectively have advantage.
Summary of the invention
The present invention carries out pre-service with these two kinds of digestion methods to the scrap rubber grain respectively in test, and analyze and research, contrast with orthogonal test, and the detection by ICP, thereby find out a kind of feasible sample pretreating method.The invention provides following technical scheme:
The digestion method of the best in a kind of waste colloidal particle heavy metal measurement is characterized in that comprising wet method and dry method mensuration, and wherein wet method is undertaken by following step:
(1) accurately take by weighing the waste and old colloidal particles sample 0.2g of particle diameter 0.5-1mm, place small beaker respectively, each adds nitration mixture 6-10ml, and on the electric hot plate about 180-200 ℃ hot digestion 1-2 hour, put coldly, obtain clear solutions;
(2) with the unnecessary sour evaporate to dryness of above-mentioned digestion solution, be cooled to room temperature, add the dense HNO of 0.5ml
3, the dissolving back is transferred to constant volume in the 10ml color comparison tube with deionized water, with ICP-AES content of beary metal is measured; Described nitration mixture is by HNO
3, HClO
4And H
2SO
4Form:
Dry method is measured:
(1) preliminary test:
Accurately take by weighing about 4 kinds of each 0.2g of varigrained micelle two parts, place porcelain crucible respectively, place muffle furnace, temperature is controlled at 600 ℃ and 800 ℃ respectively, and its effect is observed in calcination 4 hours;
(2) orthogonal test:
On the basis of preliminary test, select micelle with 4-6mm, be principal element with ashing temperature, ashing time, sour kind, design three factors, three water-glass L
9(3
3) carry out orthogonal test;
(3) accurately take by weighing 9 parts on 0.2g sample, place in the porcelain crucible, test.
The method of the invention, wherein nitration mixture HNO
3, HClO
4And H
2SO
4W/v be: HNO
3:: H
2SO=1: 1: 4, digestion time was 1 hour, and temperature is controlled at 190 ℃.
The method of the invention, wherein four of waste and old colloidal particles kinds of different dynamics micelles are respectively 0.5-1mm, 1-2mm, 2-4mm or 4-6mm.
Embodiment
For simple and purpose clearly, hereinafter appropriate omission the description of known technology, in order to avoid those unnecessary details influences are to the description of the technical program.Below in conjunction with preferred embodiment, the present invention will be further described.
Embodiment 1
Accurately take by weighing the waste and old colloidal particles sample 0.2g of particle diameter 0.5mm, place small beaker respectively, each adds nitration mixture 6ml, and hot digestion is 1 hour on the electric hot plate about 180 ℃, puts coldly, obtains clear solutions; (2) with the unnecessary sour evaporate to dryness of above-mentioned digestion solution, be cooled to room temperature, add the dense HNO of 0.5ml
3, the dissolving back is transferred to constant volume in the 10ml color comparison tube with deionized water, with ICP-AES content of beary metal is measured, and ZnO can record its content through the digestion sample.Secondly, the content of Fe is also higher, and Mn, Cu, Pb, Cd all contain.Wherein nitration mixture is by HNO
3, HClO
4And H
2SO
4=1: 1: 4.By wet method digestion, adopt ICP-AES that content of beary metal is measured, Zn content is higher, secondly is Fe, and Mn, Cu, Pb, Cd all contain.The recovery is 95%.
Embodiment 2
Accurately take by weighing the waste and old colloidal particles sample 0.2g of particle diameter 2mm, place small beaker respectively, each adds nitration mixture 10ml, and hot digestion is 1 hour on the electric hot plate about 190 ℃, puts coldly, obtains clear solutions; (2) with the unnecessary sour evaporate to dryness of above-mentioned digestion solution, be cooled to room temperature, add the dense HNO of 0.5ml
3, the dissolving back is transferred to constant volume in the 10ml color comparison tube with deionized water, with ICP-AES content of beary metal is measured, and ZnO can record its content through the digestion sample.Secondly, the content of Fe is also higher, and Mn, Cu, Pb, Cd all contain.Wherein nitration mixture is by HNO
3, HClO
4And H
2SO
4=1: 1: 4.By wet method digestion, adopt ICP-AES that content of beary metal is measured, Zn content is higher, secondly is Fe, and Mn, Cu, Pb, Cd all contain.The recovery is 101%.
Embodiment 3
Accurately take by weighing the waste and old colloidal particles sample 0.2g of particle diameter 4mm, place small beaker respectively, each adds nitration mixture 1Oml, and hot digestion is 1 hour on the electric hot plate about 180 ℃, puts coldly, obtains clear solutions; (2) with the unnecessary sour evaporate to dryness of above-mentioned digestion solution, be cooled to room temperature, add the dense HNO of 0.5ml
3, the dissolving back is transferred to constant volume in the 10ml color comparison tube with deionized water, with ICP-AES content of beary metal is measured, and ZnO can record its content through the digestion sample.Secondly, the content of Fe is also higher, and Mn, Cu, Pb, Cd all contain.Wherein nitration mixture is by HNO
3, HClO
4And H
2SO
4=1: 1: 4.By wet method digestion, adopt ICP-AES that content of beary metal is measured, Zn content is higher, secondly is Fe, and Mn, Cu, Pb, Cd all contain.The recovery is 99%.
Embodiment 4
Instrument: ICP-AES, analytical balance, controllable temperature electric hot plate, muffle furnace, crucible, 10ml color comparison tube, transfer pipet
Reagent: HClO
4, HNO
3, H
2SO
4, HCl, H
2O
2(it is pure to be analysis)
Sample: (micelle of four kinds of different dynamics is respectively 0.5-1mm to waste and old colloidal particles, 1-2mm, 2-4mm, 4-6mm.
Experimental technique:
(1) all glass apparatus is cleaned., take out after 48 hours with 1: 3 HNO3 solution immersion, use distilled water flushing earlier, use cleaned standby seam again deionized water rinsing 2-3 time.
(2) porcelain crucible is cleaned.HCl solution with 1: 4 boiled 1 hour, took out, and cooling is used distilled water and deionized water rinsing 2-3 time successively, cleaned.Put it into drying in oven, transfer in the muffle furnace calcination to constant weight, stand-by.
(3) wet digestion method also claims wet ashing technique, promptly destroys organic sample with the oxidation of acid with strong oxidizing property or strong oxidizer, and element to be measured is existed with soluble form.
Assay method
(1) selection of nitration mixture kind
Accurately take by weighing about the waste and old colloidal particles sample 0.2g of 0.5-1mm 25 parts, place small beaker respectively, each adds nitration mixture 6ml, and hot digestion is 1 hour on the electric hot plate about 180-200 ℃, observe phenomena.Nitration mixture is followed successively by: HCl-HNO
3, 1: 1,1: 2,1: 3,1: 4,2: 1,3: 1,4: 1; HNO
3-HClO
4, 1: 1,1: 2,1: 3,1: 4,2: 1,3: 1,4: 1; HNO
3-H
2O
2, 1: 1,1: 2,1: 3,1: 4,2: 1,3: 1,4: 1; HNO
3-HClO
4-H
2SO
4, 1: 1: 1,1: 1: 2,1: 1: 3,1: 1: 4,1: 2: 1,1: 3: 1,1: 4: 1,2: 1: 1,3: 1: 1,4: 1: 1.
(2) orthogonal test
On the basis that nitration mixture is selected, determine with HNO
3, HClO
4And H
2SO
4Acid mixture is digestion solution, further arrives the research of digestion time, digestion temperature, thereby determines a kind of digestion method of the best.With nitration mixture ratio, digestion time, three factors of digestion temperature, design three factors, three water-glass L
9(3
3), see Table 1.Accurately take by weighing about 0.5-1mm micelle sample 0.2g 9 parts, place small beaker respectively, test.
Table 1L
9(3
3) orthogonal test factor level table
(3) under optimum experimental condition, varigrained scrap rubber grain is carried out digestion trial
Accurately take by weighing about 4 kinds of each 0.2g of varigrained micelle, do a parallel laboratory test for every group simultaneously.Clear up test according to optimum experimental condition.
(4) the ICP-AES method is to the mensuration of contents of heavy metal elements
Unnecessary sour evaporate to dryness with above-mentioned digestion solution is cooled to room temperature, adds the dense HNO of 0.5ml
3, the dissolving back is transferred to constant volume in the 10ml color comparison tube with deionized water, with ICP-AES content of beary metal is measured.
Embodiment 4
Dry method digestion measuring principle:
The dry ashing method is to utilize the heat energy decomposition samples, makes element to be measured become the preprocess method of solvable state.
(1) preliminary test
Accurately take by weighing about 4 kinds of each 0.2g of varigrained micelle two parts, place porcelain crucible respectively, place muffle furnace, temperature is controlled at 600 ℃ and 800 ℃ respectively, and its effect is observed in calcination 4 hours.
(2) orthogonal test
On the basis of preliminary test, select micelle with 4-6mm, be principal element with ashing temperature, ashing time, sour kind, design three factors, three water-glass L
9(3
3) carry out orthogonal test, see Table 2.
Accurately take by weighing 9 parts on 0.2g left and right sides sample, place in the porcelain crucible, test.
Table 2L
9(3
3) orthogonal test factor level table
Development results is analyzed:
(1) selection result of wet method digestion condition
By the repeatedly selectivity experiment of nitration mixture, the result shows HNO
3-HClO
4-H
2SO
4More complete to sample digestion, all obtain clear solutions.And employing HNO
3-H
2O
2The digestion sample, micelle still is an original state.Adopt chloroazotic acid, micelle digestion not exclusively.Adopt HNO
3-HClO
4Digestion needed sample could be cleared up fully in 4 hours.
Separately to HNO
3-HClO
4-H
2SO
4This group experiment is analyzed, and clears up speed three parts of sample HNO faster
3With NClO
4Volume ratio be 1: 1.In view of the above, add the acid amount and only change H separately
2SO
4Amount gets final product HNO
3: HClO
4=1: 1.Orthogonal experiments sees Table 3.
Table 3L
9(3
3) the orthogonal experiments table
By the test scoring, by the covariance analysis result, the primary and secondary of each factor is: B＞C＞A, promptly digestion time digests temperature, the nitration mixture ratio.Optimum test condition is: the ratio of acid is HNO
3: HClO
4: H
2SO
4=1: 1: 4 (volume), digestion time are 1 hour, and the digestion temperature is 190 ℃.With this understanding, the waste and old colloidal particles sample can be dissolved fully.
(2) dry method result
The result shows by dry analysis, and the micelle digestion effect of 4-6mm is better, and 600 ℃ of digestion of 800 ℃ of ratios fully.Orthogonal experiments sees Table 4.
Table 4L
9(3
3) the orthogonal experiments table
By test, scoring, by the covariance analysis result, the primary and secondary of each factor is: C＞B＞A, i.e. acid, ashing time, ashing temperature.Optimum experimental condition is: dense HNO
3The dissolving ash content, the ashing time is 4 hours, the ashing temperature is controlled at 800 ℃.With this understanding, the waste and old colloidal particles sample can obtain complete ashing.
(3) mensuration of the content of beary metal of wet method digestion.The results are shown in Table 5.
Mensuration (the unit: μ g/g) of the content of beary metal of table 5 wet method digestion
From the ICP-AES measurement result as can be seen in the heavy metal element, the content of Zn is higher.Through inspection information as can be known, during producing, rubber industry use zinc paste as vulcanizing activator, its effect is exactly the effect of giving full play to organic accelerator, reduce accelerator dosage or shorten cure time, zinc paste adds in the rubber except that the effect with sulfurate activity, with the effect of sulfuration, reinforcement, increase-volume.Therefore, residual ZnO can record its content through the digestion sample.Secondly, the content of Fe is also higher, and Mn, Cu, Pb, Cd all contain.
(4) development conclusion
In China; the comprehensive utilization of waste old is that the problem of solution rapidly is badly in need of in present environmental protection, and waste old processing or powder essence are become varigrained micelle, can be applicable to railway, physical culture runway, sound-proof wall etc.; but not only salvaging has crucial meaning to environmental protection simultaneously.
The digestion of this The thesis wet method and two kinds of digestion methods of dry ashing carry out sample pretreatment to waste and old colloidal particles.By a large amount of tests, the result shows, waste and old colloidal particles is preferably adopted wet method digestion, and effect is better.
Dry method digestion elapsed time is long, and in podzolic process, some heavy metal element has partial loss, and measurement result is caused error simultaneously.
By the analysis of wet method digestion orthogonal test, the best is cleared up condition and is: HNO
3: HCl0
4: H
2SO
4=1: 1: 4 (volume), digestion time are 1 hour, and temperature is controlled at 190 ℃.
By wet method digestion, adopt ICP-AES that content of beary metal is measured, Zn content is higher, secondly is Fe, and Mn, Cu, Pb, Cd all contain.The recovery is 92%-101%.
The present invention is after the preferred embodiment that describes in detail, being familiar with this technology personage can be well understood to, can carry out various variations and modification not breaking away under above-mentioned claim and the spirit, all foundations technical spirit of the present invention all belongs to the scope of technical solution of the present invention to any simple modification, equivalent variations and modification that above embodiment did.And the embodiment that the present invention also is not subject in the instructions to be given an actual example.
Claims (2)
1. the digestion method of determining heavy metals in the scrap rubber grain is characterized in that wet method undertaken by following step:
(1) accurately take by weighing the waste and old colloidal particles sample 0.2g of particle diameter 0.5-1mm, place small beaker respectively, each adds nitration mixture 6-10ml, and on 180-200 ℃ electric hot plate hot digestion 1-2 hour, put coldly, obtain clear solutions;
(2) with the unnecessary sour evaporate to dryness of the settled solution that obtains in the above-mentioned steps (1), be cooled to room temperature, add the dense HNO of 0.5ml
3, the dissolving back is transferred to constant volume in the 10ml color comparison tube with deionized water; Described nitration mixture is by HNO
3, HClO
4And H
2SO
4Form.
2. the described digestion method of claim 1, wherein nitration mixture HNO
3, HClO
4And H
2SO
4Volume ratio be HNO
3: HClO
4: H
2SO
4=1: 1: 4, digestion time was 1 hour, and temperature is controlled at 190 ℃.
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|---|---|---|---|
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| CN107589108A (en) * | 2017-10-27 | 2018-01-16 | 贵州航天精工制造有限公司 | A kind of method of metal oxide content in measure rubber |
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