AU615189B2 - Process for preparing active coke from brown coal - Google Patents
Process for preparing active coke from brown coal Download PDFInfo
- Publication number
- AU615189B2 AU615189B2 AU16308/88A AU1630888A AU615189B2 AU 615189 B2 AU615189 B2 AU 615189B2 AU 16308/88 A AU16308/88 A AU 16308/88A AU 1630888 A AU1630888 A AU 1630888A AU 615189 B2 AU615189 B2 AU 615189B2
- Authority
- AU
- Australia
- Prior art keywords
- brown coal
- coke
- moulded bodies
- coking
- active coke
- 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.)
- Ceased
Links
- 239000000571 coke Substances 0.000 title claims description 44
- 239000003077 lignite Substances 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000000034 method Methods 0.000 claims description 19
- 238000001179 sorption measurement Methods 0.000 claims description 16
- 238000004939 coking Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000006835 compression Effects 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- 230000002000 scavenging effect Effects 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 12
- 239000011148 porous material Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000003245 coal Substances 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000001994 activation Methods 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 2
- 235000010447 xylitol Nutrition 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011287 low-temperature tar Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
- C01B32/384—Granulation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 Form COMPLETE SPECIFICATION
(ORIGINAL)
FOR OFFICE USE615 189 Short Title: Int. Cl; Application Number: Lodged: Complete Specification-Lodged: Accepted: *too Lapsed: too. Published: 99 *o 0 Priority: 9 Related Art: TO BE COMPLETED BY APPLICANT 9te0 0 0 0 Name of Applicant: VEB GASKOMBINAT "FRITZ SELBMANN" o SCHWARZE PUMPE Address of Applicant: Schwarze Pumpe, DDR 7610, EAST GERMANY I Actual Inveitor: Wolfgang Heschel; Erhard Klose; Hans-Jurgen Kopischke; Gunter Muller; S.Wolfgang Naundorf; Fritz Schkommodau; o Gunter Scholz; Horst Wundes Address for Service: GRIFFITH HACK CO 71 YORK STREET SYDNEY NSW 2000 Complete Specification for the invention entitled: SPROCESS FOR PREPARING ACTIVE COKE FROM BROWN COAL ~The following statement is a full description of this T invention, including the best method of performing it known to me/us:- 3184G/MS _I The invention relates to a process for preparing active coke from brown coal for use as an adsorption agent in gas purification especially for desulphuriz?tion cf flue gases. The active coke prepared according to ':he invention can be used in travelling layer adsorbers.
Carbon adsorption is characterized by active coke which, compared to conventional active coal, has a small specific surface (200 m 2/g) only, however has great mechanical strength and a large adsorption capacity for
SO
2 The greiat mechanical strength (abrasive resistance and resistance to compression) must be constant for an economical operation of the travelling layer adsorber in the desulphurization of flue gas including the regeneration of loaded adsorbent.
et i* 15 Processes for the preparation of such active coke are known. DE-OS 26 24 663 (West German published patent application) discloses a process according to which adsorption cokes with an adjustable variable pore system and high solidity are formed by agglomeration of fine-particled carbonaceous base materials, with the addition of plastics which act as binders. Starting from a mixture of oxidized coking coal and butadiene/acrylonitrile mixed polymerisate, an activated coke is produced which is suitable as an adsorption agent in flue gas desulphurization.
It is also known that active coke for SO adsorption can be made from mineral coal whilst an inactive particle consisting of ceramic material is surrounded by active coke particles (WO 85/04347). Patent Specification WO 85/04388 discloses a process and a device for the *30 preparation of active form coke on the basis of pretreated mineral coal. A common feature of the conventional active coke prepartion processes is the use of a binding agent, wherein this is mixed with the finely divided starting materials and moulded articles are produced which are thermally aftertreated. A disadvantage is the number of essential process steps which cause high operational costs and result in an expensive product.
7921S/MS -2 0O
S
4~
V
S
VS
V V ~t V rV~' V. V V I~
V
V V V. V
V.
*.IV
V
.V.4
V
V S
V.
DD-WP 252 550 (East German economic patent) discloses a process for the preparation of carbon molecular sieves frcin bro-wn coal in which the pore system can only be adjusted by the choice of raw material, the defined preparation of raw material, the briquetting conditions and the coking regime tailored for the type of raw material.
These carbon molecular sieves can however only be used conditionally for the So 2 adsorption as their specific surface is too small.
The present invention therefor'e provides a technically and economically advantageous preparation of active coke from brown coal for use in adsorptive gas purification, especially in desulphurization of flue g~gs.
To this end, the invention provides a process for 15 preparing abrasion resistant, granular active coke on the basis of brown coal, which enables in a technologically simple maanner at a defined pore system, the production, of a high specific surface, without the need to add mineral coal and binding agents.
According to the invention there is provided a process for preparing active coke from brown coal for use as an adsorption agent, especially for desulphurization of flue gases, wherein brown coal having a moisture content of 6-11 wt% and a particle size of less than 0.2 mm, i8 compressed to moulded articles at a pressure of 20-50 MPa, if necessary b r employing auxiliary compaction means~, the moulded bodies are subsequently reduced to a particle size of less than 2 tit, the obtained particles are again compressed to moulded bodies at a pressure of from 140 to 250 MPa and the moulded 30 bodies are coked at a coking temperature of from 650 to 800*C at a heat-up rate of from 0.8 to 1.2 K/mmn in a temperature range of from 50 to 350'C, and 2 to 5 K/mmn in a temperature range of fr-om 350 to 800*C, and where the coking is carried out in a scavenging gas containing 10-30 vol% CO 2 and 10-40 vol% ste.im at a residenco time of 1-3 hours.
The size of the pores is controlled by the kind of preparation of raw material, the conditions of briquetting 3and the coking regime. It is essential for the invention that the coking is carried out in an atmosphere containing Co 2and steam and in the stated temperature range.
The result is that the walls of the pores are freed from still sticking pyrolysis residues, surface oxides and chemically adsorbed gases, so that the adsorption efficiency of the specific =v-face is increased and the accessibility of the entire pore system is improved, without participation of the carbon of the coke structure in the reaction. This is achieved in that the coking treatment is carried out in a scaven~ging gas atmosphere, wherein the treatment te~mperature is controlled within a specified range,. Under the indicated temperature conditions the structure and the strength of the active coke is retained.
There does not appear to be any burning of the carbon structure such as in the preparation of active coke by means 4 of gas activation of BHT-coke, (where "BHT-coke" refers to a "lignite high temperature coke" or a "brown coal high temperature coke"), where burning of more than 40 Ma-% occurs.
It can therefore be seen that the present invention provides a process in which the type anid manner of raw material upgrading and agglomeration (two-stage "V agglomeration process) causes a pore structure to be produced which is favourable for the use of coke granulate as adsorption coke.
This is due tco the controlled pyrolysis of the agglomerates in a gas atmosphere comprising steam and carbon dioxide. Activation in the sense of an increase in the 6'3 adsorption capacity, in particular for SO 2 and NOR, is .2 detectable. It is essential here that the agents, water vapour and CO 2 are in contact with the forming coke during the entire pyrolysis process. This pre vents the formation of secondary coke (due to cracKing processes in the low temperature tar) which would otherwise be deposited in the pores (particularly micro-pores) and would prevent A access to these pores by SO 2 NOX or other adsorption 792 iS/MS- 4 media.
The pyrolysis process carried out according to the invention renders superfluous the otherw: !e necessary activation process (partial carboh gasification) of the coke subsequent to pyrolysis. A further ensential advantage of the process according to the inventio is that, under the stated conditions, only the secondary coke deposits are removed; the process does no 4 however, lead to partial gasification of the carbon of the primary coke (which is critical in maintaining the solidity of the adsorption coke).
Embodiment The invention will now be further described by means o e of 4 examples: 15 Example 1 oo Raw miocene brown coal poor in xylite having the composition (d-basis) ash 7 Ma% volatile components 51 Ma% coke yield 49 Ma% fixed carbon 42 Ma% is according to the invention, compressed to moulded bodies, *e which in a scavenging gas atmosphere consisting of 10 vol%
CO
2 and 15 vol% H20 D is coked according to the o.04 0 a following regime: to 300°C 1.2 K/min 200 to 1000"C 3 K/min residence time 2 hours o :o30 The thus treated moulded bodies are cooled in inert gas and reduced to a particle size of from 5 to 8 mm. The granulate is activated in a packet bed with an SO 2 containing gas under the following conditions.
Composition of gas in vol%: So 2
H
2 0:5; 02: 5; N2 as residue adsorption temperature: 1801C 7921S/MS 5 r
A
ti specific gas loading (at 180°C): 730 h The abrasion resistance of the active coke granulate was determined in a ROCA drum (where "ROCA drum" refers to a sieve (filter) strainer and a test/assay/examination drum for coke), (weight of samp section 3mm).
Final temperature of coking Residence time at 100% desulphurization (h) Degree of desulphurization after 6h
SO
2 treatment after 6h 15 Resistance to abrasion flash point Le 30 g, 1000 revolutions, sieve 640 4.7 82 5.5 9.5.3 230 725 5.2 98 6.2 94.4 240 800 4.8 95 5.8 94 255 850 3.9 87 5.3 95 260 1000 0.1 20 x) 0. 9 x) 270 0 00 0 004 0 0a aa00 6 00 a00 00 0 0 0 0 s 0 0 1 a tI a 00001 i 0 a 00, Go 0 a 00 00 0 a 006 o o 00 0 0< *000 Example 2 The adsorption behaviour of indus 1 hammer) and high temperature coke pyrolysis briquettes (Gaskombinat relative to sulphur dioxide under
BHT
Residence time at 100% 25 desulphurization (h) Degree of desulphurization after 6h
SO
2 loading after 6h Resistance to abrasion 30 Flash point trially made BHT (HT coke) of so Schwarze Pumpe) the conditions of Exeample 1.
coke HT coke 0.1 0 22 100 x coke (Launch called very hard were tested 2.2 90 250 0.8 x 270 Note: x) after 2.5 hours Example 3 Raw eocene brown coal poor in xylite and rich in tar having the composition (d-basis) 7921S/MS 6 ash 18.5 Ma% volatile components 53.0 Ma% coke yield 47.0 Ma% fixed carbon 28.5 Ma% is compressed according to the process of the invention into moulded bodies by the addition of 4 Ma% sulphite waste liquor having a solid content of 36 Ma% as auxiliary granulating means.
they are then coked according to Example 1 and loaded with SO 2 Final temperature of coking 600 700 750 o800 Residence time at 100% Sdesulphurization 0.3 0.9 4.3 4 4 Degree of desulphuri- 49 86 92 83 81 o 1o zation after 6h o t r 15 SO 2-treatment after 6h 4.8 5.4 5.5 5.4 5.4 Resistance to abrasion 97.5 98 97 97 98 SFlash point 220 230 250 250 260 Example 4 Industrially prepared brown coal low temperature coke (BTT-coke, which is brown coal low temperature coke Schwelerei Deuoen) and an activate (fire waste 24 Ma%) recovered throughout by gas t It activation at 850°C, are loaded under the conditions of Example 1 Oo. with SO 2 (particle size 1 to 2 mm) a 0 o 0 BTT coke activate Residence time at 100% 1.3 4.6 Degree of desulphurization 0 0 after 6h 39 i 2- loading after 6h 4.3 7921S/MS 7
Claims (4)
1. Process for preparing active coke from brown coal for use as an adsorption agent, wherein brown coal having a moisture content of 6-11 wt% and a particle size of less than 0.2 mm, is compressed into moulded bodies at a pressure of 20-50 MPa, the moulded bodies are subsequently reduced to a particle size of less than 3 mm, the obtained particles are again compressed into moulded bodies at a pressure from 140 to 250 MPa and the moulded bodies are coked at a coking temperaure of from 650 to 800°C at a heat-up rate of from 0.8 to 1.2 K/min in a temperature range of from 50 to 350°C and 2 to 5 K/min in a temperature range of from 350 to 0, 800°C, and wherein the coking is carried out in a scavenging o a 1 15 gas containing 10-30 vol% CO and 10-40 vol% steam at a residence time of 1-3 hours. 00 01 a 9 a
2. Process as claimed in claim 1, wherein a means for colt aiding initial compression of the brown coal into moulded bodies is employed.
3. Process as claimed in claim 1, wherein the means for a aiding initial compression of the brown coal is sulphite o0 waste liquor. a 0 oo 0
4. Process substantially as herein described with a0o reference to any one of Examples 1 to 4. 07 0 30 DATED this 4th day of June 1990 VEG GASKOMBINA': "FRITZ SELBMANN" SCHWARZE PUMPE By their Patent Attorneys GRIFFITH HACK CO. 792 IS/MS 8
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD30342887A DD266035B5 (en) | 1987-06-02 | 1987-06-02 | Process for the production of activated coke from lignite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU1630888A AU1630888A (en) | 1988-12-08 |
| AU615189B2 true AU615189B2 (en) | 1991-09-26 |
Family
ID=5589525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU16308/88A Ceased AU615189B2 (en) | 1987-06-02 | 1988-05-17 | Process for preparing active coke from brown coal |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS6487507A (en) |
| AU (1) | AU615189B2 (en) |
| DD (1) | DD266035B5 (en) |
| DE (1) | DE3807393A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69412398T2 (en) * | 1993-09-14 | 1999-04-15 | Kuraray Chemical Co., Ltd., Bizen, Okayama | Deodorant containing metal oxide and containing activated carbon |
| JP5300390B2 (en) * | 2007-09-27 | 2013-09-25 | 太平工業株式会社 | Active coke for exhaust gas treatment process of moving bed system with excellent durability |
| CN115651712B (en) * | 2022-10-28 | 2025-07-18 | 国家能源集团宁夏煤业有限责任公司 | Device and method for co-producing hydrogen-rich synthesis gas and active carbon, and active carbon |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU523490B2 (en) * | 1977-12-30 | 1982-07-29 | Carborundum Company, The | Activated carbon |
| AU523419B2 (en) * | 1977-12-02 | 1982-07-29 | Carborundum Company, The | Activated carbon made from brown coal |
| AU5223486A (en) * | 1985-02-01 | 1986-08-07 | Cra Services Limited | Production of activated carbon |
-
1987
- 1987-06-02 DD DD30342887A patent/DD266035B5/en not_active IP Right Cessation
-
1988
- 1988-03-07 DE DE3807393A patent/DE3807393A1/en not_active Withdrawn
- 1988-05-17 AU AU16308/88A patent/AU615189B2/en not_active Ceased
- 1988-06-02 JP JP63134548A patent/JPS6487507A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU523419B2 (en) * | 1977-12-02 | 1982-07-29 | Carborundum Company, The | Activated carbon made from brown coal |
| AU523490B2 (en) * | 1977-12-30 | 1982-07-29 | Carborundum Company, The | Activated carbon |
| AU5223486A (en) * | 1985-02-01 | 1986-08-07 | Cra Services Limited | Production of activated carbon |
Also Published As
| Publication number | Publication date |
|---|---|
| DD266035A1 (en) | 1989-03-22 |
| AU1630888A (en) | 1988-12-08 |
| DE3807393A1 (en) | 1989-09-21 |
| DD266035B5 (en) | 1994-07-28 |
| JPS6487507A (en) | 1989-03-31 |
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