CN103143551B - Original form dechroming method for chrome leather fragment, and application of product thereof in fertilizer aspect - Google Patents
Original form dechroming method for chrome leather fragment, and application of product thereof in fertilizer aspect Download PDFInfo
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Abstract
The invention relates to an original form dechroming method for chrome leather fragment, and application of a product thereof in fertilizer aspect. The method comprises the following steps of: adding water and calcium oxide, soaking at 20-40 DEG C for 1-4 days, washing by water and filtering; adding water, acid and salt into the filter residue, dechroming at 20-30 DEG C for 2-4 hours, washing by water and filtering; continuing to add water, salt and alkaline into the filter residue, keeping the temperature and dechroming for 30-60 min, regulating the pH to be neutral, washing by water and filtering; obtaining an original form dechromed product of chrome leather fragment; mixing and crushing the original form dechromed product of chrome leather fragment with plant ash, pelleting, and thus containing an agricultural composite fertilizer. The composite fertilizer not only has low chrome content and is rich of potassium element and organic nitrogen, but also has certain slow release function, and can effectively promote growth of plants.
Description
Technical field
The present invention relates to method and the application of product in production fertilizer thereof that chrome shavinge original shape state takes off chromium.
Background technology
After the fast development that experienced by 30 years leather industries, China has become universally acknowledged leather big country, leather industry is also after paper industry and brewery industry simultaneously, become the third-largest pollution industry, annual discharge tanning sewage about 8000 ~ 12,000 ten thousand tons, produce containing chromium scurf skin slag 30 ~ 400,000 tons, wherein main exist with the form of chrome shavinge, therefore, how the focus that shavings becomes industry concern is recycled effectively and rationally.
Along with the fast development of China's agricultural, the kind of agricultural fertilizer is also more and more diversified.From the angle regulating edaphon and promotion agricultural sustainable development, fertilizer is still the focus of fertilizer product development and application.The exploitation of fertilizer is while ensureing sufficient nutritional labeling, and reducing costs also is very actual problem.
Zhang Peng etc. (see: a kind of method [P] utilizing leather castoff Preparation of amino acid, small molecular peptide composite organic fertilizer and chromium to regain. China: CN201010556326.4. 2011.8.17.) tanning waste through de-chromium process is hydrolyzed into protein and peptide and amino acid, then obtains fertilizer by concentrate drying.But this technique is not analyzed chromium content in hydrolysate, and those skilled in the art do not know its application security.Meanwhile, the hydrolysate obtained is liquid, and drying process is complicated, and granulation is restricted, and production application cost is higher, is not suitable for applying.
Nitrogen abundant in chrome shavinge can become effective nutritional labeling of fertilizer, if a kind of method with low cost can be found carry out de-chromium to chrome shavinge, and after de-chromium, do not cause chrome shavinge that a large amount of hydrolysis occurs, so all have great importance to the research and development of the recycling of chrome shavinge in fertilizer and novel organic fertilizer.
Summary of the invention
The present invention aims to provide method and the application of product in production fertilizer thereof that a kind of chrome shavinge original shape state takes off chromium, screens suitable technological parameter by processing step reasonable in design, to solve the problem be hydrolyzed in a large number after current chrome shavinge takes off chromium.
The present invention is by the following technical solutions:
Chrome shavinge original shape state takes off the method for chromium, it is characterized in that, the following step carries out:
1) weigh the raw material of following weight proportion: chrome shavinge 1 part, 5 ~ 10 parts, water, 0.1 ~ 0.2 part, calcium oxide, soak 1 ~ 4 day under 20 ~ 40 DEG C of conditions, then washing filtering, obtains a filter residue;
2) in a described filter residue, add 4 ~ 7 weight parts waters, 0.8 ~ 1 weight portion acid and 0.1 ~ 0.2 parts by wt NaCl, under 20 ~ 30 DEG C of conditions, constant temperature takes off chromium 2 ~ 4h, then washing filtering, obtains secondary filter residue;
3) in described secondary filter residue, add 5 ~ 10 weight parts waters, the alkali of 0.1 ~ 0.2 weight portion, 0.1 ~ 0.2 parts by wt NaCl, the de-chromium 30 ~ 60min of insulation under 20 ~ 30 DEG C of conditions, then regulate pH to neutral, washing filtering, obtains three filter residues; Obtain chrome shavinge original shape state after being dried by described three filter residues and take off chromium product.
Described acid refers to sulfuric acid and oxalic acid according to quality than sulfuric acid: the mixed acid that oxalic acid 1:2 ~ 4 mix; Described alkali is any one in NaOH, magnesia.
Described three filter residues dry employing two step seasoning; First low temperature drying 3 ~ 5h under 60 ~ 70 DEG C of conditions, makes moisture reach less than 20%; Carry out high temperature drying more afterwards, control temperature 110 ~ 120 DEG C, dry 40 ~ 70min.
The method gained end-product that described chrome shavinge original shape state takes off chromium is producing the application in fertilizer, it is characterized in that, described chrome shavinge original shape state is taken off chromium product to be ground into Powdered, mix with plant ash according to the ratio of weight ratio 7:7 ~ 3, then press the granulation of 8mm particle size, obtain described fertilizer;
At the beginning of described crushing process divides, pulverizing and broken two steps of fine powder are carried out, that is: the first step, takes off chromium product by described chrome shavinge original shape state and be ground into the coarse granule that granularity is 6 ~ 8mm; Second step, is ground into Powdered by described coarse granule further.
Beneficial effect of the present invention is:
(1) the present invention selects the cheap chemicals such as acid, alkali, salt for de-Cr materials, can reduce production cost, be conducive to the marketing of product.
(2) the shavings chromium content after de-chromium is low, after testing, meets the requirement to chromium content≤150ppm in fertilizer national standard.
(3) in de-chromium process, shavings percent hydrolysis is low, and hold its shape state substantially, is convenient to drying and the granulation operations of product.Simultaneously original shape state takes off chromium and remains part collagen fiber structure in shavings, makes fertilizer product have certain slow-release function.
Detailed description of the invention
In order to understand better and implement the present invention, further illustrate the present invention below in conjunction with specific embodiment.
embodiment 1
Weigh chrome shavinge 50g, calcium oxide 5g, distilled water 500mL, after fully stirring, 30 DEG C of heat-insulation soaking 2d, period needs often to stir to ensure that chrome shavinge fully disperses; Washing filtering, adds distilled water 350mL, 5g sodium chloride, oxalic acid 10g and concentrated sulfuric acid 15mL, fully stirs in filter residue, 25 DEG C of de-chromium 2h of insulation, washing filtering; Continue in filter residue, add 350mL distilled water, 5g sodium hydroxide alkali and 8g sodium chloride, under 25 DEG C of conditions after the de-chromium 40min of insulation, regulate pH to neutral, fully wash, filter; Obtain chrome shavinge original shape state after being dried by filter residue and take off chromium product.
Drying course adopts two step seasonings: first low temperature drying 3h under 60 ~ 70 DEG C of conditions, makes moisture reach less than 20%; Carry out high temperature drying more afterwards, control temperature 110 ~ 120 DEG C, dry 70min.
Take chrome shavinge original shape state take off chromium product 70g pulverize after, add plant ash 70g, fully mix, then press the granulation of 8mm particle size, obtain described fertilizer; At the beginning of described crushing process divides, pulverizing and broken two steps of fine powder are carried out, that is: the first step, takes off chromium product by described chrome shavinge original shape state and be ground into the coarse granule that granularity is 6 ~ 8mm; Second step, is ground into Powdered by described coarse granule further.
embodiment 2
Weigh chrome shavinge 50g, calcium oxide 7g, distilled water 250mL, after fully stirring, 40 DEG C of heat-insulation soaking 1d, period needs often to stir to ensure that chrome shavinge fully disperses; Washing filtering, adds distilled water 300mL, 6g sodium chloride, oxalic acid 15g and concentrated sulfuric acid 15mL, fully stirs in filter residue, 30 DEG C of de-chromium 3h of insulation, washing filtering; Continue in filter residue, add 250mL distilled water, 7g NaOH and 5g sodium chloride, under 20 DEG C of conditions after the de-chromium 30min of insulation, regulate pH to neutral, fully wash, filter; Obtain chrome shavinge original shape state after being dried by filter residue and take off chromium product.
Drying course adopts two step seasonings: first low temperature drying 4h under 60 ~ 70 DEG C of conditions, makes moisture reach less than 20%; Carry out high temperature drying more afterwards, control temperature 110 ~ 120 DEG C, dry 60min.
Take chrome shavinge original shape state take off chromium product 70g pulverize after, add plant ash 30g, fully mix, then press the granulation of 8mm particle size, obtain described fertilizer; At the beginning of described crushing process divides, pulverizing and broken two steps of fine powder are carried out, that is: the first step, takes off chromium product by described chrome shavinge original shape state and be ground into the coarse granule that granularity is 6 ~ 8mm; Second step, is ground into Powdered by described coarse granule further.
embodiment 3
Weigh chrome shavinge 50g, calcium oxide 10g, distilled water 400mL, after fully stirring, 20 DEG C of heat-insulation soaking 4d, period needs often to stir to ensure that chrome shavinge fully disperses; Washing filtering, adds distilled water 200mL, 10g sodium chloride, oxalic acid 10g and concentrated sulfuric acid 20mL, fully stirs in filter residue, 20 DEG C of de-chromium 4h of insulation, washing filtering; Continue in filter residue, add 500mL distilled water, 10g magnesia and 10g sodium chloride, under 60 DEG C of conditions after the de-chromium 60min of insulation, regulate pH to neutral, fully wash, filter; Obtain chrome shavinge original shape state after being dried by filter residue and take off chromium product.
Drying course adopts two step seasonings: first low temperature drying 5h under 60 ~ 70 DEG C of conditions, makes moisture reach less than 20%; Carry out high temperature drying more afterwards, control temperature 110 ~ 120 DEG C, dry 40min.
Take chrome shavinge original shape state take off chromium product 70g pulverize after, add plant ash 50g, fully mix, then press the granulation of 8mm particle size, obtain described fertilizer; At the beginning of described crushing process divides, pulverizing and broken two steps of fine powder are carried out, that is: the first step, takes off chromium product by described chrome shavinge original shape state and be ground into the coarse granule that granularity is 6 ~ 8mm; Second step, is ground into Powdered by described coarse granule further.
Beneficial effect of the present invention is further illustrated below by relevant experimental data:
The hydrolysis situation percent hydrolysis of chrome shavinge, nitrogen recovery and de-chromium rate are weighed, and result is as table 1.
Table 1 chrome shavinge original shape state takes off chromium statistical effect table
| Experimental group | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Percent hydrolysis/% | 10.4 | 16.7 | 18.4 |
| Nitrogen yield/% | 88.2 | 80.6 | 74.2 |
| De-chromium rate/% | 94.2 | 97.6 | 98.4 |
In table 1, the computing formula of percent hydrolysis is:
In formula, M
sample---the initial mass of hydrolysis substrate, g;
M
filter residue---the quality after the oven dry of hydrolysate suction filtration filter residue, g.
The computing formula of nitrogen yield is:
Wherein, the mensuration of nitrogen content measures according to QB/T2722-2005.
The formula of de-chromium rate is:
Wherein, the mensuration of chromium content is according to QB/T2720-2005 operation.
As shown in Table 1, use original shape state dechromium method while reaching higher de-chromium rate, shavings form is not affected substantially, and nitrogen nutrition loss is less.
Fertilizer prepared by this experiment is used for the fertilising of soybean planting process, is weighed the performance of organic fertilizer product by indexs such as nitrogen content, potassium content, chromium content and slowly-releasing cycles (lixiviate in 25 DEG C of hydrostatic of nitrogen element starts the time to reaching needed for 80% nutrients accumulation release rate).Take plant ash as blank group.Result statistics is as table 2.
Table 2 fertilizer performance indications
| Experimental group | Blank group | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Nitrogen content/% | 1.4 | 8.1 | 9.0 | 8.7 |
| Potassium (K 2O) content/% | 7.3 | 3.5 | 3.0 | 3.2 |
| Phosphorus (P 2O 3) content/% | 2.6 | 1.6 | 1.7 | 2.0 |
| Chromium (Cr 2O 3) content/ppm | 10 | 121 | 124 | 143 |
| Slowly-releasing cycle/moon | 1.4 | 7.8 | 9.4 | 8.5 |
In table 2, nitrogen content measures according to QB/T2722-2005, and chromium content measures according to QB/T2720-2005, and potassium content, phosphorus content and slowly-releasing cycle measure according to NY525-2012.The nitrogen content of this fertilizer, potassium content, the index such as phosphorus content and chromium content meet the requirement to fertilizer nutriment in NY525-2012, and meanwhile, visible compared with blank, this fertilizer has certain slow-release function.
Claims (3)
1. chrome shavinge original shape state takes off the method gained end-product of chromium producing the application in fertilizer, it is characterized in that,
Described chrome shavinge original shape state takes off the method for chromium, carries out according to the following step:
1) weigh the raw material of following weight proportion: chrome shavinge 1 part, 5 ~ 10 parts, water, 0.1 ~ 0.2 part, calcium oxide, soak 1 ~ 4 day under 20 ~ 40 DEG C of conditions, then washing filtering, obtains a filter residue;
2) in a described filter residue, add 4 ~ 7 weight parts waters, 0.8 ~ 1 weight portion acid and 0.1 ~ 0.2 parts by wt NaCl, under 20 ~ 30 DEG C of conditions, constant temperature takes off chromium 2 ~ 4h, then washing filtering, obtains secondary filter residue;
3) in described secondary filter residue, add 5 ~ 10 weight parts waters, the alkali of 0.1 ~ 0.2 weight portion, 0.1 ~ 0.2 parts by wt NaCl, the de-chromium 30 ~ 60min of insulation under 20 ~ 30 DEG C of conditions, then regulate pH to neutral, washing filtering, obtains three filter residues; Obtain chrome shavinge original shape state after being dried by described three filter residues and take off chromium product;
Described chrome shavinge original shape state is taken off chromium product to be ground into Powdered, mixes with plant ash according to the ratio of weight ratio 7:7 ~ 3, then presses the granulation of 8mm particle size, obtains described fertilizer;
At the beginning of described crushing process divides, pulverizing and broken two steps of fine powder are carried out, that is: the first step, takes off chromium product by described chrome shavinge original shape state and be ground into the coarse granule that granularity is 6 ~ 8mm; Second step, is ground into Powdered by described coarse granule further.
2. chrome shavinge original shape state as claimed in claim 1 takes off the method gained end-product of chromium producing the application in fertilizer, it is characterized in that, described acid refers to sulfuric acid and oxalic acid according to quality than sulfuric acid: the mixed acid that oxalic acid 1:2 ~ 4 mix; Described alkali is any one in NaOH, magnesia.
3. chrome shavinge original shape state as claimed in claim 1 takes off the method gained end-product of chromium producing the application in fertilizer, it is characterized in that, described three filter residues dry employing two step seasoning; First low temperature drying 3 ~ 5h under 60 ~ 70 DEG C of conditions, makes moisture reach less than 20%; Carry out high temperature drying more afterwards, control temperature 110 ~ 120 DEG C, dry 40 ~ 70min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103525574A (en) * | 2013-10-24 | 2014-01-22 | 山东全杰皮革研究所有限公司 | Method for preparing washing surfactant by utilizing tanning waste chrome shavings |
| CN108570105A (en) * | 2018-04-24 | 2018-09-25 | 陕西科技大学 | Acid system takes off method and the application of chromium extraction collagen |
| CN112592223B (en) * | 2018-05-18 | 2022-07-22 | 烟台大学 | Preparation method of leaf fertilizer raw material by using tanning chromium-containing leather scraps |
| CN108424291B (en) * | 2018-06-01 | 2021-02-05 | 烟台大学 | Preparation method for preparing amino acid liquid surface fertilizer raw material from tanning chromium-containing leather scraps |
| CN109052877B (en) * | 2018-08-02 | 2021-04-13 | 广州桑尼环保科技有限公司 | Method and system for recycling chromium sludge resources and harmlessly treating waste residues |
| CN113061062B (en) * | 2021-03-22 | 2022-02-18 | 四川大学 | Method for preparing short peptide-growth-promoting bacterium compound fertilizer by dechromization fermentation of wet blue dander and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4100154A (en) * | 1977-04-22 | 1978-07-11 | A. L. Gebhardt Company | Process for recovery and separation of nutritious protein hydrolysate and chromium from chrome leather scrap |
| US4401573A (en) * | 1980-05-12 | 1983-08-30 | Luigi Stoppani S.P.A. | Continuous process for the removal of chromium from waste waters and valorization of the recovered chromium |
| US4483829A (en) * | 1982-02-02 | 1984-11-20 | Giuliano Guardini | Process for recovering proteins and chromium from chrome-tanning waste |
| CN1041547A (en) * | 1988-10-17 | 1990-04-25 | 中国科学院生态环境研究中心 | Chrome leather slag comprehensive utilization method and product |
| CN102153378A (en) * | 2010-11-24 | 2011-08-17 | 北京化工大学 | Method for preparing amino acid and small molecular peptide composite organic fertilizer and recycling chromium from leather waste |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5819610B2 (en) * | 1973-03-09 | 1983-04-19 | ニツソウエンジニアリング カブシキガイシヤ | name change |
| JPS6055000B2 (en) * | 1983-03-28 | 1985-12-03 | 和歌山県 | How to remove chrome from chrome tanned leather scraps |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4100154A (en) * | 1977-04-22 | 1978-07-11 | A. L. Gebhardt Company | Process for recovery and separation of nutritious protein hydrolysate and chromium from chrome leather scrap |
| US4401573A (en) * | 1980-05-12 | 1983-08-30 | Luigi Stoppani S.P.A. | Continuous process for the removal of chromium from waste waters and valorization of the recovered chromium |
| US4483829A (en) * | 1982-02-02 | 1984-11-20 | Giuliano Guardini | Process for recovering proteins and chromium from chrome-tanning waste |
| CN1041547A (en) * | 1988-10-17 | 1990-04-25 | 中国科学院生态环境研究中心 | Chrome leather slag comprehensive utilization method and product |
| CN102153378A (en) * | 2010-11-24 | 2011-08-17 | 北京化工大学 | Method for preparing amino acid and small molecular peptide composite organic fertilizer and recycling chromium from leather waste |
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