CN1039801C - Manufacturing method of low-sulfur expansible black lead - Google Patents
Manufacturing method of low-sulfur expansible black lead Download PDFInfo
- Publication number
- CN1039801C CN1039801C CN93119757A CN93119757A CN1039801C CN 1039801 C CN1039801 C CN 1039801C CN 93119757 A CN93119757 A CN 93119757A CN 93119757 A CN93119757 A CN 93119757A CN 1039801 C CN1039801 C CN 1039801C
- Authority
- CN
- China
- Prior art keywords
- graphite
- weight
- black lead
- parts
- consumption
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention relates to a preparing method of low-sulfur expansible black lead, which belongs to the chemical treatment of black lead. The present invention adopts the method: sulfuric acid and soluble peroxydisulfate are respectively and orderly used for soaking natural scale black lead; centrifugation deacidification is carried out; the natural scale black lead is put in mixed solution of nitric acid and oxalic acid; after being washed by water, the natural scale black lead is baked at low temperature until water content is smaller than 1%; after the natural scale black lead is expanded, low-sulfur expansible black lead is prepared. The black lead is suitable for making various sealing members, etc., and is difficult to generate corrosion to sealing surface metal. The method reduces environmental pollution and has the advantages of easy mastery and stable product quality.
Description
The present invention relates to a kind of manufacture method of low-sulfur expansible black lead, belong to the chemical treatment of graphite.
The preparation expansible black lead mostly adopts chemistry and electrolysis process at present.Chemical process is that natural flake graphite be impregnated in the mixed solution of 100-105 ℃ the concentrated nitric acid and 98% the vitriol oil, reacts 1-3 hour, and being washed to PH then is 3-6.60-100 ℃ of oven dry down, under 900-1000 ℃, carry out expansion process again, produce the vermiform expanded graphite.The shortcoming of this method is: use the mixed solution of the vitriol oil and concentrated nitric acid easily to produce obnoxious flavoures such as acid mist and operational hazards down at 100-105 ℃.And contain the sulphur of 2-3% in the expanded graphite that makes of this method.In order to overcome the shortcoming of aforesaid method, having occurred publication number again is the patent of JP63112408, the kish that is about to generate in the smelt iron process be dipped in dissolved persulphate, concentration in the sulphuric acid soln 95% or more, through wash, after the drying, expand more than 200 ℃ expansible black lead.This kind method has the following disadvantages: (1) does not propose to increase the measure of persulphate at the concentrated sulfuric acid dissolution degree, causes the serious waste of peroxydisulfate.(2) propose to reduce effective chemical process of sulphur content in the expansible black lead.(3) acid consumption is big.(4) the sulphur content height of expansible black lead, allowance for expansion is little.
The object of the present invention is to provide the manufacture method that a kind of sulphur content is low, consume energy less, pollute little expansible black lead.
The object of the present invention is achieved like this:
Method of the present invention comprises:
A, oxidation: crystalline flake graphite is immersed in 45-60 ℃ the vitriol oil (concentration 90%-98%, consumption is 2.5-5 a times of graphite parts by weight) in, stir, the peroxydisulfate (consumption is 0.1-0.23 a times of graphite parts by weight) that under constantly stirring, adds solubility again, reaction times is: 0.5-3 hour, temperature of reaction is 45-60 ℃, makes acid graphite.
B: desulfurization: with the centrifugal depickling of acid graphite after the oxidation (the depickling amount by adding sulfuric acid parts by weight 0.6-0.9 doubly) after insert nitric acid (concentration be 65%-68%, consumption be the graphite parts by weight 0.5-1.1 doubly) and the mixed solution of oxalic acid (consumption is 0.02-0.07 a times of used graphite parts by weight), stir, arrest reaction 2-6 hour, temperature of reaction is 25-30 ℃, the centrifugal depickling of reacted graphite, water are washed behind pH value 4-7, centrifuge dripping;
C, expanded: the graphite after the desulfurization is dry under 40-60 ℃ temperature, and water content is controlled at the 0.5%-1% parts by weight, carries out expanded at last under 900-950 ℃.
The optional one of the following of solubility peroxydisulfate: ammonium peroxydisulfate, Sodium persulfate, Potassium Persulfate.The optimum amount of solubility peroxydisulfate is 0.15-0.18 a times of graphite parts by weight.The optimum amount of oxalic acid is 0.03-0.05 a times of graphite parts by weight.
The sulfuric acid liquid that reclaims after the oxidation can repeatedly recycle, and promptly adds sulfuric acid (concentration is 90%-98%, and consumption is former 0.1-0.4 times with the sulfuric acid parts by weight) and ammonium peroxydisulfate (consumption is 0.1-0.15 a times of graphite parts by weight) in the sulfuric acid liquid that reclaims.In addition, the mixed solution that adds bicarbonate of ammonia (consumption is 0.5-1.2 a times of graphite parts by weight) generation ammonium sulfate and ammonium nitrate in the dilute acid soln that is produced is washed in desulfurization.
Compared with the prior art the present invention has following significant advantage: one, the expansible black lead sulphur content that this production process is made is low.Its two, reduced environmental pollution, it is low to consume energy.This method is simple in addition, is easy to grasp constant product quality.
Now, the present invention is further elaborated with following specific embodiment.Used graphite is natural flake graphite in the example.
Embodiment 1: it is that 50 ℃, weight are in sulfuric acid (concentration the is 98%) solution of 40 grams that 10 gram graphite are immersed in temperature, after stirring, adds the solid ammonium peroxydisulfates of 1.5 grams again under constantly stirring.Reacted 40 minutes, temperature of reaction is 50 ℃.After question response is finished, with the acid graphite centrifugal desulfurizing that makes, after sloughing the sulfuric acid of 33 grams, the mixed solution that adds 10 gram nitric acid (concentration is 65%) and 0.5 gram oxalic acid again, stir, arrest reaction 3 hours, temperature of reaction is 25 ℃, and with the centrifugal depickling of reacted graphite, water washes after pH value is 6, centrifuge dripping, and 60 ℃ down dry, be 0.8% of graphite parts by weight until water content, expanded 50 seconds through 950 ℃ high temperature again, can produce allowance for expansion is 220 milliliters/gram, and sulphur content is 0.8% expansible black lead.For reducing cost, can repeatedly recycle the sulfuric acid liquid that reclaims after the oxidation, promptly in the sulfuric acid liquid that reclaims, add sulfuric acid (concentration is 90%-98%, and consumption is former 0.1-0.4 times with the sulfuric acid parts by weight) and ammonium peroxydisulfate (consumption is 0.1-0.15 a times of graphite parts by weight).In addition, the mixed solution that adds bicarbonate of ammonia (consumption is 0.5-1.2 a times of graphite parts by weight) generation ammonium sulfate and ammonium nitrate in the dilute acid soln that is produced is washed in desulfurization.
Embodiment 2: compare with embodiment 1, difference is that used sulfuric acid amount is 35 grams, and temperature is 55 ℃, adds the solid Sodium persulfate of 1.7 grams, reacts 1 hour, sloughs the sulfuric acid of 31 grams, and consumption of oxalic acid is 0.3 gram, and the arrest reaction time is 4 hours.Make sulphur content and be 0.5% expansible black lead.
Embodiment 3: compare with embodiment 1, difference is that used temperature is 45 ℃, adds the Potassium Persulfate of 2.1 grams, reacts 50 minutes, sloughs the sulfuric acid of 30 grams, and nitric acid dosage is 11 grams, and consumption of oxalic acid is 0.4 gram, and the arrest reaction time is 3.5 hours.Making allowance for expansion is 225 milliliters/gram, and sulphur content is 0.52% expansible black lead.
Claims (6)
1, a kind of manufacture method of low-sulfur expansible black lead, it includes oxidation, desulfurization, puffing operation, it is characterized in that:
A, oxidation: crystalline flake graphite is immersed in 45-60 ℃ the vitriol oil, the concentration of the vitriol oil is 90%-98%, its consumption is 2.5-5 a times of graphite parts by weight, stir, under constantly stirring, add the peroxydisulfate that consumption is the 0.1-0.23 solubility doubly of graphite parts by weight again, reaction times is: 0.5-3 hour, temperature of reaction was 45-60 ℃, made acid graphite;
B: desulfurization: with the centrifugal depickling of acid graphite after the oxidation, its depickling amount by adding sulfuric acid parts by weight 0.6-0.9 doubly, after insert the mixed solution of nitric acid and oxalic acid, wherein the concentration of nitric acid is 65%-68%, its consumption is 0.5-1.1 a times of graphite parts by weight, the consumption of oxalic acid is 0.02-0.07 a times of graphite parts by weight, stirs arrest reaction 2-6 hour, temperature of reaction is 25-30 ℃, the centrifugal depickling of reacted graphite, water are washed behind pH value 4-7, centrifuge dripping;
C, expanded: the graphite after the desulfurization is dry under 40-60 ℃ temperature, and water content is controlled at the 0.5%-1% parts by weight, carries out expanded at last under 900-950 ℃.
2, method according to claim 1 is characterized in that the optional one of the following of said solubility peroxydisulfate: ammonium peroxydisulfate, Sodium persulfate, Potassium Persulfate.
3, method according to claim 2, the optimum amount that it is characterized in that said solubility peroxydisulfate are 0.15-0.18 times of graphite parts by weight.
4, method according to claim 3, the optimum amount that it is characterized in that said oxalic acid are 0.03-0.05 times of graphite parts by weight.
5, according to claim 1 or 2 or 3 or 4 described methods, it is characterized in that the sulfuric acid liquid that reclaims after the oxidation can repeatedly recycle, promptly in the sulfuric acid liquid that reclaims, add sulfuric acid and ammonium peroxydisulfate, wherein vitriolic concentration is 90%-98%, its consumption is former 0.1-0.4 times with the sulfuric acid parts by weight, and the consumption of ammonium peroxydisulfate is 0.1-0.15 a times of graphite parts by weight.
6, method according to claim 4, adding consumption in the dilute acid soln that it is characterized in that the desulfurization washing is produced is the 0.5-1.2 bicarbonate of ammonia doubly of graphite parts by weight, generates the mixed solution of ammonium sulfate and ammonium nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93119757A CN1039801C (en) | 1993-11-05 | 1993-11-05 | Manufacturing method of low-sulfur expansible black lead |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93119757A CN1039801C (en) | 1993-11-05 | 1993-11-05 | Manufacturing method of low-sulfur expansible black lead |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1102398A CN1102398A (en) | 1995-05-10 |
| CN1039801C true CN1039801C (en) | 1998-09-16 |
Family
ID=4993062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93119757A Expired - Fee Related CN1039801C (en) | 1993-11-05 | 1993-11-05 | Manufacturing method of low-sulfur expansible black lead |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1039801C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100400416C (en) * | 2006-07-11 | 2008-07-09 | 河北农业大学 | Process for preparing expandable graphite with high reference expansion temperature |
| CN106450312B (en) * | 2016-10-18 | 2019-05-14 | 福建翔丰华新能源材料有限公司 | A kind of preparation method of inorganic doping modified natural graphite |
| CN108069419B (en) * | 2017-12-21 | 2020-02-21 | 浙江山峪科技股份有限公司 | Macroscopic graphene aerogel and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63112408A (en) * | 1986-10-31 | 1988-05-17 | Sumitomo Metal Ind Ltd | Production of thermally expanded kish graphite |
| JPS63195104A (en) * | 1987-02-06 | 1988-08-12 | Nippon Kasei Kk | Production of thermally expandable graphite |
-
1993
- 1993-11-05 CN CN93119757A patent/CN1039801C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63112408A (en) * | 1986-10-31 | 1988-05-17 | Sumitomo Metal Ind Ltd | Production of thermally expanded kish graphite |
| JPS63195104A (en) * | 1987-02-06 | 1988-08-12 | Nippon Kasei Kk | Production of thermally expandable graphite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1102398A (en) | 1995-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111575480A (en) | Method for processing cobalt intermediate product | |
| GB1501701A (en) | Method of removing nitrogen oxides from a gas containing nitrogen oxides | |
| CN102060395B (en) | Method for treating complex chemical wastewater by combination of Fenton and starch-based flocculant | |
| CN1039801C (en) | Manufacturing method of low-sulfur expansible black lead | |
| CN1195102C (en) | Acid pickling promotor for iron and steel | |
| CN101451244A (en) | Novel method for removing iron rust on steel device by using concentrated hydrochloric acid or concentrated sulfuric acid | |
| CN108046229A (en) | A kind of method of battery-grade anhydrous iron phosphate synthesis desulfurating | |
| CN112010758A (en) | Triethylamine recovery method | |
| CN1224693A (en) | Chemical graft process to prepare expansive graphite | |
| CN1239071A (en) | Process for preparing flake-shaped expanded graphite | |
| CN1075312A (en) | The production method of humic acid liquid compound fertilizer | |
| CN1050340C (en) | Prodn process of no-sulphur expansion graphite | |
| CN1096767A (en) | A kind of method of making low-sulfur expansible black lead with chemical method | |
| US5173157A (en) | Method for processing residual fixing-baths | |
| CN1052961C (en) | Method for producing ammonium sulfate by using waste ammonia water | |
| CN112110470A (en) | Phosphogypsum waste residue treatment method | |
| CN112063247A (en) | Phosphorus-free prefilming agent for industrial circulating cooling water system and preparation method thereof | |
| CN105561981B (en) | A kind of derived energy chemical spent lye processing high-efficiency desulfurization catalyst and preparation method thereof | |
| CN85104742B (en) | Process of rust removing and passivating for iron and steel | |
| CN105836813B (en) | Method for preparing polymeric ferric sulfate | |
| JPS5493669A (en) | Treating method for desulfurized waste liquid of coke oven gas | |
| CN1935654A (en) | Method for producing ammonia sulfate utilizing titanium white waste acid | |
| CN108796483A (en) | Vitrified agent and preparation method thereof and application method | |
| CN1073965A (en) | A kind of acid sludge comprehensive utilization method | |
| CN114870903B (en) | Mixed catalyst for dissolving trace colloidal iron in water vapor of power station |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |