Method for further processing of carbon raw material

Abstract

Process for further use of a water-containing carbon raw material comprising the treatment of the carbon raw material with carbon dioxide or water vapor or a mixture thereof at elevated temperature and the admixing of the thus obtained carbon material with an acid.

Claims

1. A process, comprising: treating with carbon dioxide, water vapor, or a mixture of both, at a temperature of 1100° C. or less, a carbon raw material obtained from quench water of an acetylene synthesis, to obtain a treated carbon material with an increased specific surface area; and mixing the treated carbon material with an acid, to obtain a product carbon material, wherein the carbon raw material has a water content of 55 to 85 wt. % based on a total carbon raw material mass, and a sulfur content of less than 0.05 percent based on a total dry mass of the carbon raw material, and wherein the product carbon material has a specific surface area in a range of from 500 to 2000 m.sup.2/g.

2. The process of claim 1, wherein the product carbon material has an iron content less than 0.018 wt. %, based on the total dry mass.

3. The process of claim 1, wherein the carbon raw material has a nickel content of less than 0.006 wt. %, based on the total dry mass of the carbon raw material.

4. The process of claim 1, wherein the treating comprises treating the carbon raw material with the carbon dioxide.

5. The process of claim 1, further comprising: adjusting the water content of the carbon raw material by drying.

6. The process of claim 1, wherein the acid comprises hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, oxalic acid, and/or acetic acid.

7. The process of claim 1, wherein the acid comprises hydrochloric acid and/or sulfuric acid.

8. The process of claim 1, wherein the acid comprises hydrochloric acid.

9. The process of claim 1, wherein the product carbon material has a sodium content of less than 0.02 wt. % and/or an iron content of less than 0.025 wt. %, based on the total dry mass.

10. The process of claim 1, wherein the product carbon material has an iodine number in a range of from 700 mg/g to 1200 mg/g.

11. The process of claim 1, wherein the carbon raw material has a specific surface area in a range of from 100 to 400 m.sup.2/g.

12. The process of claim 1, wherein the carbon raw material has a nitrogen content of less than 1.5 wt. %, based on the total dry mass.

13. The process of claim 1, wherein the carbon raw material is green coke.

14. The process of claim 1, further comprising, prior to the treating: sedimenting the quench water, comprising carbonaceous material, from the acetylene synthesis, to separate off and feed the carbonaceous material to the treating as the carbon raw material.

15. The process of claim 14, further comprising: dewatering the carbonaceous material after the sedimenting and before feeding the carbonaceous material to the treating as the carbon raw material.

16. The process of claim 1, wherein the carbon raw material has a water content of 40 to 85 wt. %, based on the total carbon raw material mass.

17. The process of claim 1, wherein the carbon raw material has a water content of 50 to 85 wt. %, based on the total carbon raw material mass.

18. The process of claim 1, further comprising: adjusting the water content of the carbon raw material by adding another carbon material.

19. The process of claim 1, further comprising: adjusting the water content of the carbon raw material by drying; and adjusting the water content of the carbon raw material by adding another carbon material.

Description

EXAMPLES

(1) Methods of Determination:

(2) Specific surface area was determined according to DIN ISO 9277:1995.

(3) Determination of carbon, hydrogen, nitrogen by elemental analysis:

(4) Method: The sample was combusted in a helium atmosphere with addition of oxygen and by means of a thermal conductivity detector NO.sub.x was determined after conversion into N.sub.2, carbon was determined as CO.sub.2 and hydrogen was determined as H.sub.2O.

(5) Reagents:

(6) Reaction gas: oxygen

(7) Carrier gas: helium

(8) Combustion catalyst: CuO

(9) Reduction catalyst: Cu

(10) Sample Preparation:

(11) 1 to 5 mg of the sample were weighed in under a standard atmosphere. The sample was subsequently placed in a CHN analyzer (carbon, hydrogen, nitrogen).

(12) Measurement Parameters:

(13) Combustion temperature: about 1100° C.

(14) Reduction temperature: about 700° C.

(15) Determination of Sulfur by Elemental Analysis:

(16) Method: The sample was combusted in a helium-oxygen stream (conversion of S to SO.sub.2). SO.sub.2 was detected by means of a thermal conductivity detector.

(17) Reagents:

(18) Reaction gas: oxygen

(19) Carrier gas: helium

(20) Combustion catalyst: Cu, WO.sub.3 on Al.sub.2O.sub.3

(21) Additives 2:1 m/m V.sub.2O.sub.5/WO.sub.3

(22) Sample Preparation:

(23) 1 to 5 mg of the sample were weighed in under a standard atmosphere. The sample was subsequently placed in a sulfur analyzer.

(24) Measurement Parameters:

(25) Combustion temperature: about 1030° C.

(26) Carrier gas pressure: about 100 kPa

(27) Determination of Fe, Ni, Na:

(28) The sample was admixed with concentrated sulfuric acid and heated to 300° C. After evaporation of the sulfuric acid the residue is admixed with a mixture comprising concentrated nitric acid, concentrated perchloric acid and concentrated sulfuric acid and mineralized with gentle warming. The procedure is generally complete when all organic constituents have been oxidized. The acids are removed by further heating and the thus obtained residue is taken up in dilute hydrochloric acid. The thus obtained solution is subsequently analyzed by atomic spectrometry methods, ICP-OES.

(29) The ash content was determined according to ASTM D2866-11

(30) The iodine number was determined according to ASTM D4607 (1999).

(31) Specifications of the employed carbon raw material:

(32) Origin: acetylene water quench process

(33) Carbon content: 96 percent based on the total dry mass of the carbon raw material

(34) Water content: 70 weight percent based on the total mass

(35) Sulfur content: 0.02 percent based on the total dry mass of the carbon raw material

(36) Nitrogen content: <0.7 percent based on the total dry mass of the carbon raw material

(37) Sodium content: 0.23 percent based on the total dry mass of the carbon raw material

(38) Iron content: 0.19 percent based on the total dry mass of the carbon raw material

(39) Nickel content: <0.004 percent based on the total dry mass of the carbon raw material

(40) Specific surface area: from 200 to 300 m.sup.2/g

Comparative Example 1: Treatment of the Carbon Raw Material with Water

(41) The carbon raw material was manually comminuted. A 200 g sample was initially charged and made up to 550 ml with demineralized water having a temperature of 100° C. The dispersion was separated using a sieve. The sample was subsequently comminuted again and rinsed with a further 200 ml of demineralized water. The obtained dispersion was stirred for one hour at 300 rpm under reflux. The dispersion was subsequently filtered and rinsed with a further 500 ml of hot demineralized water. A sample of 1.9 g was dried to a constant weight for analysis. The sample was dried at 80° C.

(42) Sodium content: 0.12 percent based on the total dry mass

(43) Iron content: 0.19 percent based on the total dry mass

Comparative Example 2: Treatment of the Carbon Raw Material with Hydrochloric Acid

(44) The carbon raw material was manually comminuted. A 200 g sample was initially charged and made up to one liter with demineralized water. The dispersion was admixed with 10 ml of hydrochloric acid (37%) and with stirring (300 rpm) heated for one hour under reflux conditions. The dispersion was subsequently filtered and the residue rinsed with a further 500 ml of hot demineralized water. The filter cake was subsequently dispersed in one liter of demineralized water and with stirring (300 rpm) heated for one hour under reflux conditions. The dispersion was filtered and rinsed again with demineralized water (50° C. to 70° C.) until a pH of 7 was established in the washing water. A sample of 1.9 g was dried to a constant weight for analysis. The sample was dried at 80° C.

(45) Sodium content: 0.10 percent based on the total dry mass

(46) Iron content: 0.18 percent based on the total dry mass

Example 1: Treatment of the Carbon Raw Material with Water Vapor

(47) 30 kg of carbon raw material were heated to 900° C. in a tubular oven under nitrogen. A heating rate of 10 K/min was employed. 10 minutes after attainment of the target temperature the gas stream was switched over and within a period of one hour comprised 50% water vapor and 50% nitrogen. The thus obtained carbon material was then cooled under a nitrogen atmosphere.

(48) The specific surface area of the thus obtained carbon material was 987 m.sup.2/g.

Example 2: Treatment of the Carbon Raw Material with Carbon Dioxide

(49) 602 mg of carbon raw material were heated to 900° C. in a thermogravimetry apparatus under argon. A heating rate of 10 K/min was employed. 20 minutes after attainment of the target temperature the gas stream was switched over and within a period of two hours comprised 90% carbon dioxide and 10% argon. The thus obtained carbon material was then cooled under an argon atmosphere.

(50) The specific surface area of the thus treated carbon material was 987 m.sup.2/g.

Comparative Example 3: Treatment of the Thus Obtained Carbon Material with Water

(51) The carbon material treated with water vapor or carbon dioxide was manually comminuted. A 200 g sample was initially charged and made up to 550 ml with demineralized water having a temperature of 100° C. The dispersion was separated using a sieve. The sample was subsequently comminuted again and rinsed with a further 200 ml of demineralized water. The obtained dispersion was stirred for one hour at 300 rpm under reflux. The dispersion was subsequently filtered and rinsed with a further 500 ml of hot demineralized water. A sample of 1.9 g was dried to a constant weight for analysis. The sample was dried at 80° C.

(52) Sodium content: 0.031 percent based on the total dry mass

(53) Iron content: 0.3 percent based on the total dry mass

Example 3: Treatment of the Thus Obtained Carbon Material with Hydrochloric Acid

(54) The carbon material treated with water vapor or carbon dioxide was manually comminuted. A 200 g sample was initially charged and made up to one liter with demineralized water. The dispersion was admixed with 10 ml of hydrochloric acid (37%) and with stirring (300 rpm) heated for one hour under reflux conditions. The dispersion was subsequently filtered and the residue rinsed with a further 500 ml of hot demineralized water. The filter cake was subsequently dispersed in one liter of demineralized water and with stirring (300 rpm) heated for one hour under reflux conditions. The dispersion was filtered and rinsed again with demineralized water (50° C. to 70° C.) until a pH of 7 was established in the washing water. A sample of 1.9 g was dried to a constant weight for analysis. The sample was dried at 80° C.

(55) Sodium content: 0.013 percent based on the total dry mass

(56) Iron content: 0.009 percent based on the total dry mass

(57) Nickel content: <0.004 percent based on the total dry mass

(58) Ash content: 1.32 percent based on the total dry mass

(59) BET: 900 to 1000 m.sup.2/g

(60) Iodine number: 854 mg/g

(61) As is apparent from the examples it is possible to obtain from the carbon raw material in the present process a carbon material having a sodium content of 0.013 and an iron content of 0.009 percent based on the total dry mass.