CN103497220B - Production technology of sodium humate - Google Patents
Production technology of sodium humate Download PDFInfo
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- CN103497220B CN103497220B CN201310494632.3A CN201310494632A CN103497220B CN 103497220 B CN103497220 B CN 103497220B CN 201310494632 A CN201310494632 A CN 201310494632A CN 103497220 B CN103497220 B CN 103497220B
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- sodium hydroxide
- humic acids
- hydroxide solution
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Abstract
The invention relates to a production technology of sodium humate, and provides a technology for producing the sodium humate with brown coal or decomposed coal or peat as main raw materials. According to the technology, firstly raw materials are smashed and then put in a horizontal type stirring mixer to carry out initial oxidation to directly generate partial micromolecular humic acid, the acidizing is carried out on the mixture under acidic conditions to remove the calcium magnesium and other ions combined with the humic acid, twice alkaline filter is carried out, filter liquor is combined, secondary oxygenolysis is carried out on obtained filter residue under alkaline conditions, filter is carried out, filter residue is recycled, filter liquor is combined, sodium hydroxide solutions are added to the filter liquor, and mixing processing is carried out through an electrical heating kettle and a blender to enable full complexation to be carried out on sodium hydroxide in the filter liquor and the humic acid. After the complete complexation, sodium humate filter liquor passes through a centrifugal spray dryer to carry out dehydration on products, and final products of sodium humate is finally generated through a microwave-vacuum drying oven. The sodium humate produced by the technology can be widely applied to crop growth conditioning agents, cement water-reducing agents, drilling fluid conditioning agents, boiler water treatment agents and the like.
Description
technical field:
The present invention relates to a kind of production technology of Sodium salts humic acids, particularly a kind ofly take brown coal, weathered coal or the peat technology as main material production Sodium salts humic acids.
background technology:
Humic acids is extensively present in peat, brown coal, weathered coal, and its principal element consists of carbon, hydrogen, oxygen, nitrogen, sulphur and a small amount of phosphorus.Humic acids has good ion exchange, and its functional group is to the positively charged ion Na in soil
+, Ca
2+, Mg
2+, Fe
3+, Al
3+with negatively charged ion Cl
-, SO4
2-there are very strong exchange capacity and adsorption (complexing, chelating properties).Sodium salts humic acids adopts the natural low magnesium weathered coal of the low calcium of high-quality containing humic acids to refine and form through chemistry, and it is multi-functional macromolecular compound, contains hydroxyl, quinonyl, the active group that carboxyl etc. are more, has very large internal surface area, there is stronger absorption, exchange, complexing, sequestering power, Sodium salts humic acids is through the Chinese Academy of Sciences, the Ministry of Chemical Industry, Ministry of Coal Industry, petroleum department, the tackling key problem of the Ministry of Railways and each province and city relevant research and production department, the various fields in national economy is applied and approves.Especially as ceramic additive, dispergator, drilling mud adjusting agent, process water stablizer, cement water reducing agent, boiler detergent, ore floatation agent, waste gas waste water conditioner, water coal oar admixture, coal briquette bond, negative battery plate expander etc., demonstrate powerful vitality, obtained significant economical effectiveness, prospect is very wide.Secondly, in agricultural, as compound manure, can change Soil structure, farm crop be played to the effect of disease resistance increasing both production and income.In livestock culture, as fodder additives, in aquaculture, as synergistic agent, all obtained significant economic benefit.
Tradition Sodium salts humic acids manufacturing process is for extracting the humic acids in weathered coal with a certain proportion of sodium hydroxide solution, separated with residue after, concentrate, be dried, obtain the Sodium salts humic acids finished product of solid.Detailed process is as follows: weathered coal first carries out wet ball grinding, obtains granularity and is less than 20 object coal slurries, puts into dosing vessel, the caustic soda that adds calculated amount, control PH to 11, and liquid-solid ratio 9:1, after mixing, deliver to extracting tank, jacket steam heating, make temperature in tank be raised to 85～90 ℃, stirring reaction 0.5h, is discharged into settling tank and makes solid-liquid separation, upper clear supernate is transferred to vaporizer and is concentrated to 10Be, is pumped into spray-drying tower dry.But aforesaid method exist speed of response slow, yield poorly down, the shortcoming such as poor product quality and production cost height.Therefore, develop a kind ofly there is speed of response, output is high and the measured Sodium salts humic acids production technology of matter has important economy and social value.
summary of the invention:
For overcoming the deficiencies in the prior art, Sodium salts humic acids production technology of the present invention is according to the physicochemical characteristic of humic acids, in tradition, with weathered coal, peat and brown coal, extract in the technical foundation of processing Sodium salts humic acids, alr mode and separating device to tradition processing extraction Sodium salts humic acids have been done corresponding adjustment and improvement, in reaction process, adopt secondary oxidation to decompose and stirrer combination treatment alkalization process for electrically heated still, obtained that a kind of speed of response is fast, output is high and the Sodium salts humic acids production technology of quality of finished product good.
This technology is a kind of with brown coal, weathered coal or peat are main raw material, first by carrying out in Horizontal stirring mixing machine after raw material pulverizing, be tentatively oxidized with direct generating portion small molecules humic acids, under acidic conditions, said mixture is carried out to acidification again, to remove the calcium combining with humic acids, magnesium plasma, twice alkalization filtered rear merging filtrate and gained filter residue carried out under alkaline condition to secondary oxidation decomposition, filtered and recycled filter residue merging filtrate, add sodium hydroxide solution, through electrically heated still stirrer combination treatment, make sodium hydroxide and the abundant complexing of humic acids in filtrate.Sodium salts humic acids filtrate after complexing is dewatered to product through drying machine with centrifugal spray completely, finally by crossing microwave vacuum drying baking box, generates ultimate product Sodium salts humic acids.The Sodium salts humic acids that this technology generates can be widely used in crop growth conditioning agent, cement water reducing agent, drilling mud conditioning agent, water treating agent for boilers etc.
Sodium salts humic acids production method of the present invention comprises the steps:
1) raw material pulverizing to the 70 order left and right of humic acids will be rich in;
2) coal dust is added in Horizontal stirring mixing machine, adds oxidant hydrogen peroxide to react 30 min;
3) add ethanol solution hydrochloride, regulate pH to 1.5, three-dimensional multidirectional mixing for some time;
4) add sodium hydroxide solution, heat and be incubated for some time, filter, obtain filtrate I,
5) above-mentioned steps 4) gained filter residue after pure water rinsing, add sodium hydroxide solution, heat and be incubated for some time, filter, obtain filtrate II;
6) in above-mentioned step 5) gained filter residue, add hydrogen peroxide and sodium hydroxide solution, heat and be incubated for some time, filter, obtain filtrate II I, and reclaim filter residue;
7) merging filtrate I ~ III, adds sodium hydroxide solution, adopts electrically heated still to stir with stirrer, heating, reaction 30min;
8) above-mentioned steps 7) in reaction mixture dry in drying machine with centrifugal spray after, then carry out microwave vacuum drying, obtain Sodium salts humic acids finished product.
Wherein, the raw material that is rich in humic acids described method steps 1) is brown coal, weathered coal or peat;
Step 2) in, the concentration of hydrogen peroxide is 4.0% ~ 4.5%;
In step 3), ethanol solution hydrochloride is mixed by 15% ethanolic soln and 36% hydrochloric acid soln, and doubly, three-dimensional multinomial mixing time is 8 min ~ 10 min to the 10-15 that the volume of acidic alcohol used is raw material weight;
In step 4), the concentration of sodium hydroxide solution is 1.0%, and the 10-15 that the volume of sodium hydroxide solution used is raw material weight doubly, is heated to 45 ℃ ~ 50 ℃, and soaking time is 10min ~ 15 min;
In step 5), the concentration of sodium hydroxide solution is 1.5%, and the 10-15 that the volume of sodium hydroxide solution used is raw material weight doubly, is heated to 45 ℃ ~ 50 ℃, and soaking time is 10min ~ 15 min;
In step 6), the concentration of hydrogen peroxide is 5%, and the concentration of sodium hydroxide solution is 2.0%, and the 10-15 that the volume of sodium hydroxide solution used is raw material weight doubly, is heated to 45 ℃ ~ 50 ℃, and soaking time is 15min ~ 20 min;
In step 7), the concentration of sodium hydroxide solution is 5.0%, and doubly, stirring velocity is 1800r/min to the 5-10 that the volume of sodium hydroxide solution used is raw material weight, is heated to 45 ℃ ~ 50 ℃;
In step 8), the centrifugal spray drying time is 40min ~ 50 min, at 55 ℃ ~ 60 ℃, carries out microwave vacuum drying 1.5h.
Production method of the present invention has changed the equilibrium state on solid-liquid surface in solid-liquid reaction, has improved and has produced the speed of response of Sodium salts humic acids and the content of humic acids and quality.Thus, the unit production capacity of Sodium salts humic acids is improved, and has reduced the time of brown coal, weathered coal, peat dependence autoignition conditions disaggregation in the past, for production enterprise has reduced actual production cost.In addition, technological process of the present invention does not relate to hazardous and noxious substances, environmentally friendly.The preparation-obtained Sodium salts humic acids of the present invention is better than national standard.
accompanying drawing explanation:
Fig. 1 Sodium salts humic acids production technology whole process figure.
embodiment:
Below in conjunction with embodiment, invention is elaborated, but is not limit scope of the present invention:
embodiment 1:
The brown coal powder that is rich in humic acids is broken to 70 about orders, 50 g coal dusts are added in Horizontal stirring mixing machine, adding concentration is 4.0% hydrogen peroxide, reaction 30 min, add 500 mL ethanol solution hydrochlorides (being mixed by 15% ethanolic soln and 36% hydrochloric acid soln), regulate pH to 1.5, three-dimensional multidirectional mixing 8 min, adding concentration is 1.0% sodium hydroxide solution 500 mL, be heated to 50 ℃ and be incubated 10 min, filter, obtain filtrate I, gained filter residue is after pure water rinsing, adding concentration is 1.5% sodium hydroxide solution 500 mL, be heated to 45 ℃ and be incubated 15 min, filter, obtain filtrate II, to adding concentration in above-mentioned filter residue, be sodium hydroxide solution 500 mL that 5% hydrogen peroxide and concentration are 2%, be heated to 45 ℃ and be incubated 20 min, filter, obtain filtrate II I, and reclaim filter residue.Merging filtrate I ~ III, adding concentration is 5% sodium hydroxide solution 250 mL, adopt electrically heated still to stir with stirrer, stirring velocity is 1800r/min, is heated to 50 ℃, reaction 30min, reaction mixture is dried after 40 min in drying machine with centrifugal spray, at 55 ℃, carry out again microwave vacuum drying 1.5h, obtain Sodium salts humic acids finished product 21.8g, purity 99.1%.
embodiment 2:
The weathered coal that is rich in humic acids is crushed to 70 about orders, 100 g coal dusts are added in Horizontal stirring mixing machine, adding concentration is 4.5% hydrogen peroxide, reaction 30 min, add 1500 mL ethanol solution hydrochlorides (being mixed by 15% ethanolic soln and 36% hydrochloric acid soln), regulate pH to 1.5, three-dimensional multidirectional mixing 8 min, adding concentration is 1.0% sodium hydroxide solution 1500 mL, be heated to 45 ℃ and be incubated 15 min, filter, obtain filtrate I, gained filter residue is after pure water rinsing, adding concentration is 1.5% sodium hydroxide solution 1200 mL, be heated to 50 ℃ and be incubated 10 min, filter, obtain filtrate II, to adding concentration in above-mentioned filter residue, be sodium hydroxide solution 1500 mL that 5% hydrogen peroxide and concentration are 2%, be heated to 50 ℃ and be incubated 15 min, filter, obtain filtrate II I, and reclaim filter residue.Merging filtrate I ~ III, adding concentration is 5% sodium hydroxide solution 1000 mL, adopt electrically heated still to stir with stirrer, stirring velocity is 1800r/min, is heated to 45 ℃, reaction 30min, reaction mixture is dried after 45 min in drying machine with centrifugal spray, at 55 ℃, carry out microwave vacuum drying 1.5h again, obtain Sodium salts humic acids finished product 38.2g, purity is 99.4%.
embodiment 3:
The peat dust that is rich in humic acids is broken to 70 about orders, 100 g coal dusts are added in Horizontal stirring mixing machine, adding concentration is 4.5% hydrogen peroxide, reaction 30 min, add 1500 mL ethanol solution hydrochlorides (being mixed by 15% ethanolic soln and 36% hydrochloric acid soln), regulate pH to 1.5, three-dimensional multidirectional mixing 10 min, adding concentration is 1.0% sodium hydroxide solution 1500 mL, be heated to 45 ℃ and be incubated 15 min, filter, obtain filtrate I, gained filter residue is after pure water rinsing, adding concentration is 1.5% sodium hydroxide solution 1500 mL, be heated to 50 ℃ and be incubated 10 min, filter, obtain filtrate II, to adding concentration in above-mentioned filter residue, be sodium hydroxide solution 1200 mL that 5% hydrogen peroxide and concentration are 2%, be heated to 50 ℃ and be incubated 15 min, filter, obtain filtrate II I, and reclaim filter residue.Merging filtrate I ~ III, adding concentration is 5% sodium hydroxide solution 800 mL, adopt electrically heated still to stir with stirrer, stirring velocity is 1800r/min, is heated to 45 ℃, reaction 30min, reaction mixture is dried after 50 min in drying machine with centrifugal spray, at 60 ℃, carry out microwave vacuum drying 1.5h again, obtain Sodium salts humic acids finished product 36.2g, purity is 99.3%.
Embodiment 4:
The Sodium salts humic acids of being prepared by above-described embodiment 1-3 to gained carries out quality approach, and it is analyzed according to national standard, and acquired results is as shown in table 1 below:
The mass analysis result of table 1 embodiment 1-3 gained Sodium salts humic acids
Claims (9)
1. a production method for Sodium salts humic acids, is characterized in that comprising the steps:
1) raw material pulverizing to the 70 order left and right of humic acids will be rich in;
2) coal dust is added in Horizontal stirring mixing machine, adds oxidant hydrogen peroxide, reaction 30 min;
3) add ethanol solution hydrochloride, regulate pH to 1.5, three-dimensional multidirectional mixing for some time;
4) add sodium hydroxide solution, heat and be incubated for some time, filter, obtain filtrate I;
5) above-mentioned steps 4) gained filter residue after pure water rinsing, add sodium hydroxide solution, heat and be incubated for some time, filter, obtain filtrate II;
6) in above-mentioned step 5) gained filter residue, add hydrogen peroxide and sodium hydroxide solution, heat and be incubated for some time, filter, obtain filtrate II I, and reclaim filter residue;
7) merging filtrate I ~ III, adds sodium hydroxide solution, adopts electrically heated still, stirs heating, reaction 30min with stirrer;
8) above-mentioned steps 7) in reaction mixture dry in drying machine with centrifugal spray after, then carry out microwave vacuum drying, obtain Sodium salts humic acids finished product.
2. the production method of Sodium salts humic acids as claimed in claim 1, is characterized in that: the raw material that is rich in humic acids in step 1) is brown coal, weathered coal or peat.
3. the production method of Sodium salts humic acids as claimed in claim 1, is characterized in that: step 2) in the concentration of hydrogen peroxide be 4.0% ~ 4.5%.
4. the production method of Sodium salts humic acids as described in claim 1-3 any one, it is characterized in that: in step 3), ethanol solution hydrochloride is mixed by 15% ethanolic soln and 36% hydrochloric acid soln, the volume of acidic alcohol used is 10-15 times of raw material weight, and three-dimensional multidirectional mixing time is 8 min ~ 10 min.
5. the production method of Sodium salts humic acids as claimed in claim 1 or 2, it is characterized in that: in step 4), the concentration of sodium hydroxide solution is 1.0%, the volume of sodium hydroxide solution used is 10-15 times of raw material weight, is heated to 45 ℃ ~ 50 ℃, and soaking time is 10 min ~ 15 min.
6. the production method of Sodium salts humic acids as claimed in claim 1 or 2, it is characterized in that: in step 5), the concentration of sodium hydroxide solution is 1.5%, the volume of sodium hydroxide solution used is 10-15 times of raw material weight, is heated to 45 ℃ ~ 50 ℃, and soaking time is 10 min ~ 15 min.
7. the production method of Sodium salts humic acids as claimed in claim 1 or 2, it is characterized in that: in step 6), the concentration of hydrogen peroxide is 5%, the concentration of sodium hydroxide solution is 2.0%, the volume of sodium hydroxide solution used is 10-15 times of raw material weight, be heated to 45 ℃ ~ 50 ℃, soaking time is 15min ~ 20 min.
8. the production method of Sodium salts humic acids as described in claim 1-3 any one, it is characterized in that: in step 7), the concentration of sodium hydroxide solution is 5.0%, the volume of sodium hydroxide solution used is 5-10 times of raw material weight, and stirring velocity is 1800r/min, is heated to 45 ℃ ~ 50 ℃.
9. the production method of Sodium salts humic acids as described in claim 1-3 any one, is characterized in that: in step 8), the centrifugal spray drying time is 40min ~ 50 min, at 55 ℃ ~ 60 ℃, carries out microwave vacuum drying 1.5h.
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Cited By (1)
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| CN111560121B (en) * | 2020-04-03 | 2022-03-04 | 安徽工业大学 | Preparation method of modified lignite humic acid water reducer |
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| CN104403112A (en) * | 2014-12-04 | 2015-03-11 | 太原师范学院 | Method for quickly extracting humic acid |
| CN105111463B (en) * | 2015-08-23 | 2019-06-04 | 唐山炬能节能科技有限公司 | A method of humic acid is produced by steam explosion pre-treatment biomass |
| CN105237145B (en) * | 2015-09-01 | 2019-03-19 | 莫日根 | A kind of humic acid plants growing nutrient high-performance solid fertilizer and preparation method thereof |
| CN106279717B (en) * | 2016-11-09 | 2018-11-06 | 泸天化（集团）有限责任公司 | The preparation method of humic acid high extraction in a kind of low-order coal |
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| CN111171334A (en) * | 2020-01-21 | 2020-05-19 | 广西大学 | Method for preparing sodium humate from high-calcium magnesium ore source |
| CN116478563A (en) * | 2023-03-30 | 2023-07-25 | 哈密市神土新材料科技有限公司 | Black paint and preparation method thereof |
| CN116514610A (en) * | 2023-05-11 | 2023-08-01 | 辽宁金秋肥业有限责任公司 | Organic fertilizer process method containing high-activity humic acid |
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| CN1103339C (en) * | 1998-08-25 | 2003-03-19 | 祝亚勤 | Prepn. method of medicinal-grade peat sodium fulvic acid |
| CN1594338B (en) * | 2004-07-08 | 2010-08-04 | 哈尔滨工程大学 | Process for preparing super-strong anti-hard-water sodium (potassium) humate |
| CN101684132A (en) * | 2008-09-25 | 2010-03-31 | 唐毅 | Production method and application of humic acid and fulvic acid extracted from humus and organic salts of mineral compounds thereof |
| CN102701868A (en) * | 2012-06-27 | 2012-10-03 | 中国农业科学院农业资源与农业区划研究所 | Modified glutamic acid fertilizer synergist and production method and application thereof |
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| CN111560121B (en) * | 2020-04-03 | 2022-03-04 | 安徽工业大学 | Preparation method of modified lignite humic acid water reducer |
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