CN105000547A - Petroleum coke devulcanizing method - Google Patents
Petroleum coke devulcanizing method Download PDFInfo
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- CN105000547A CN105000547A CN201510451374.XA CN201510451374A CN105000547A CN 105000547 A CN105000547 A CN 105000547A CN 201510451374 A CN201510451374 A CN 201510451374A CN 105000547 A CN105000547 A CN 105000547A
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Abstract
The invention discloses a petroleum coke devulcanizing method. Mixing, heating and heat preserving are conducted on petroleum coke and trace catalyst in the ammonia atmosphere, and therefore the purpose of devulcanizing is achieved. The mass ratio of petroleum coke particles and compound catalyst is (10000-100):1, the temperature is raised to 700-900 DEG C, and heat preserving is conducted for 30-120 min. NiO and MoO2 with the granularity smaller than or equal to 0.1 mm are adopted in the compound catalyst, and the mass ratio of NiO and MoO2 is (4-2):1. According to the petroleum coke devulcanizing method, under the condition of not consuming much heat energy and not affecting the performance of the petroleum coke, the effect of ammonia atmosphere devulcanizing can be further improved through the means of adding the trace catalyst.
Description
Technical field
The present invention relates to a kind of method of desulfurizing petrol coke, be applied to metallurgy, material, chemical industry and environmental technology field.
Background technology
Refinery coke is the principal by product of oil refining industry, is generally obtained by delay coking process.Refinery coke is low because having ash content, and fixed carbon content high, is widely used in the fields such as metallurgy, material and chemical industry.Meanwhile, because sulfur in petroleum coke content is different, refinery coke is divided into high-sulfur (>4%), middle sulphur (2-4%) and low-sulfur Jiao (<2%).But along with deterioration and the acidifying of international crude petroleum, the quality as the refinery coke of the byproduct of oil refining is also reducing gradually, and the sulphur content especially in refinery coke is improving constantly.Sulphur content too high levels in refinery coke can affect the quality of product greatly.Meanwhile, along with the sulphur content in refinery coke increases, take refinery coke as the environmental protection pressure that the industrial enterprise of subordinate of raw material also carries more and more arduous control sulphur emissions accordingly.
Carbon anode is prepared as raw material for refinery coke.Sulphur in refinery coke mainly exists with thiophene-based aromatic hydrocarbon material, cannot remove under normal calcining temperature from refinery coke.In anode preparation process, in order to effectively remove sulphur content, the too high problem of sulphur content can only be solved with the calcining temperature improving refinery coke.Therefore, in limited reduction Behavior of High-sulfur Petroleum Coke while sulphur content, high-temperature calcination not only makes the Financial cost of calcining improve, and the casting yield of the calcined coke also reduced to a certain extent improves the anode manufacturing cost of enterprise, have impact on economic benefit.
In addition, high sulfur petroleum coke, because the high characteristic of its sulphur content, can only simply use as fuel.Under the carbon industry taking refinery coke as raw material develops the industry background more and more higher with raw petroleum coke sulphur content very fast, the production capacity breach of high-quality low-sulfur refinery coke is increasing.Therefore, how environmental protection, high sulfur petroleum coke inferior is utilized to become current carbon industry problem in the urgent need to address efficiently.
Publication application CN 104611087A utilizes ammonia calcination method to remove sulphur in refinery coke, does not relate to interpolation and the use of catalyzer.
The method of coking is avoided in the desulfurization that publication application CN 103555389 A refer to a kind of refinery coke simultaneously.But employing method is solid fuel particle, quartzy sandstone and Wingdale, in high-velocity fluidized bed combustion.Although control temperature is 850 ~ 900 DEG C, operating process needs to add quartzy sandstone and Wingdale.
Patent CN 101020854 A refer to a kind of refinery coke gasification hydrogen-producing desulfurization coupling scheme.But employing method is for adding reactor by refinery coke and sodium carbonate or salt of wormwood mixing, and passes into steam gasification.And after gasification reaction, pickling is carried out to refinery coke, washing and drying.
Patent CN 101804977 A refer to a kind of acid system and removes sulphur content technology in refinery coke.Refinery coke for refinery coke fine particle being placed in mixing acid sweetening agent certain hour at normal pressure, 0-60 DEG C, and then being isolated and washs by method.
Patent CN 101144044 A adopts a kind of sweetening agent added in refinery coke in sulfuration zirconium, cerium sulphide and yttrium sulfide to calcine, and calcining temperature employing is carried out at 1270-1500 DEG C.
Patent CN 104129774 A provides a kind of desulfurization technology.Method adds mishmetal and nitric acid-hydrochloric acid-hydrogen peroxide sweetening agent according to certain ratio of mixture under the prerequisite of refinery coke fragmentation, and then mix and stir.Again by being separated, 1300-1350 DEG C of calcining, finally obtains the refinery coke product of low sulfur content.
Summary of the invention
The object of the invention is the technology removing sulfur in petroleum coke for ammonia pyrogenic process, propose a kind of method more effectively promoting desulfuration efficiency, desulfurization degree can more than 80%.
Specific implementation process is as follows: first refinery coke is broken into 1mm and following and mix with 0.1mm grade and following composite catalyst, the mass ratio of petroleum coke particles and composite catalyst is (10000-100): 1, and then pass into ammonia, be warming up to 700-900 DEG C simultaneously and be incubated 30-120min desulfurization; Described composite catalyst is NiO and MoO adopting granularity to be less than or equal to 0.1 mm
2, NiO and MoO
2mass ratio is (4-2): 1.
Further, wherein composite catalyst is that granularity is less than or equal to 0.075 mm.
Further, the ratio that wherein petroleum coke particles mixes with composite catalyst is (5000-1000): 1.
Further, wherein the granularity of refinery coke is less than or equal to 0.5mm.
Further, wherein said desulfurization temperature is 750-850 DEG C, and soaking time is 30-60 min.
Further, wherein ammonia pressure is more than or equal to 0.101MPa.
Further, the oxide compound of nickel and molybdenum element can promote that ammonia and sulfur in petroleum coke divide the essence of reaction to be under this variable valency metal and compound existent condition thereof, sulphur content is more prone to depart from from the organic compound such as thiophene, and the active hydrogen atom produced with ammonia reacts and generates H
2s and removing in refinery coke.But in desulfurizing petrol coke, the catalytic effect of single-element is also bad, on the contrary, more than about 600 DEG C, under ammonia atmosphere, the oxide compound of mixed Ni and molybdenum element is studied discovery through us and finally can be formed one and can be expressed as MoNi
xo
x+2(x>1) complicated porous high surface area material, this material can present the effect of 1+1>2 to the desulfurizing petrol coke under ammonia atmosphere.Farthest change into this catalyzer reach with to optimum sweetening effectiveness to calcine under ammonia atmosphere in sweetening process, we determine (4-2) on a series of experiment basis: 1 this proportioning.
Outstanding feature of the present invention:
1 the present invention further significantly can reduce the sulphur content in Behavior of High-sulfur Petroleum Coke at a lower temperature compared with simple ammonia desulfurization, sulphur in refinery coke can be focused on, namely alleviate the environmental protection pressure that charcoal element produces follow-up workshop section, the sulphur removed can be made sulfur-bearing chemical again.
2 the present invention effectively can improve the utilization ratio of high sulfur petroleum coke.The further raw material use range having expanded carbon industry.
The metal oxide catalyst addition used in 3 the present invention is few, low price.
4 the invention process techniques are simple and convenient, just sulphur can be removed in the normal calcination process of raw material.
Refinery coke microtexture after 5 inventive desulfurization is substantially identical with former Jiao, and the surface tissue that the interpolation of this kind of metal catalyst is not focused damages.
Embodiment
Be described further below in conjunction with specific embodiment, but the present invention is not therefore subject to any restriction.
Embodiment 1
Get domestic certain Behavior of High-sulfur Petroleum Coke 3g, recording its sulphur content is 6.5wt.%, is crushed to 0.5 below mm, with the MoO being less than 0.075mm granularity
2be laid in the flat square porcelain boat of a 2 × 3cm after powder 0.0001g and the NiO powder 0.0002g being less than 0.075mm granularity fully mix.Then the porcelain boat containing burnt material is placed in stove, heats with the heating rate of 7 DEG C/Min, and pass into ammonia (in Reaktionsofen, ammonia pressure keeps 1 normal atmosphere), then at 800 DEG C of insulation 120min.Finally take out Jiao and carry out survey sulphur, find that wherein sulphur content is down to 1.29wt.%, desulfurization degree is 80.1%.
With comparative example 1,2,3 compare, composite catalyst with independent element catalyst and do not add any catalyzer condition under effect all to get well.As shown in table 1 in addition, change MoO under the same conditions as example 1
2with the proportioning of NiO by experiment and XRD reach a conclusion, at NiO and MoO after detecting
2mass ratio is (4-2): more easily form MoNi in the scope of 1
xo
x+2compound, and reach higher sweetening effectiveness.At NiO and MoO
2mass ratio more than 4 after, because the compound formation of the wherein Main Function of the catalyzer under equal in quality is less, effect is affected on the contrary.
Form 1
| NiO：MoO 2 | Desulfurization degree (%) |
| 1：1 | 73.5 |
| 1.5：1 | 73.7 |
| 2：1 | 80.1 |
| 3：1 | 80.7 |
| 4：1 | 80.6 |
| 4.5：1 | 73.1 |
| 5：1 | 72.1 |
Comparative example 1
Get domestic certain Behavior of High-sulfur Petroleum Coke 3g, recording its sulphur content is 6.5wt.%, is crushed to 0.5 below mm, with the MoO being less than 0.075mm granularity
2be laid in after powder 0.0003g fully mixes in the flat square porcelain boat of a 2 × 3cm.Then the porcelain boat containing burnt material is placed in stove, heats with the heating rate of 7 DEG C/Min, and pass into ammonia (in Reaktionsofen, ammonia pressure keeps 1 normal atmosphere), then at 800 DEG C of insulation 120min.Finally take out Jiao and carry out survey sulphur, find that its desulfurization degree is 69.5%.
Comparative example 2
Get domestic certain Behavior of High-sulfur Petroleum Coke 3g, recording its sulphur content is 6.5wt.%, is crushed to 0.5 below mm, is laid in the flat square porcelain boat of a 2 × 3cm after fully mixing with the NiO powder 0.0003g being less than 0.075mm granularity.Then the porcelain boat containing burnt material is placed in stove, heats with the heating rate of 7 DEG C/Min, and pass into ammonia (in Reaktionsofen, ammonia pressure keeps 1 normal atmosphere), then at 800 DEG C of insulation 120min.Finally take out Jiao and carry out survey sulphur, find that its desulfurization degree is 69.1%.
Comparative example 3
Get domestic certain Behavior of High-sulfur Petroleum Coke 3g, recording its sulphur content is 6.5wt.%, is crushed to 0.5 below mm, is laid in the flat square porcelain boat of a 2 × 3cm.Then the porcelain boat containing burnt material is placed in stove, heats with the heating rate of 7 DEG C/Min, and pass into ammonia (in Reaktionsofen, ammonia pressure keeps 1 normal atmosphere).Insulation 120min is carried out when being warming up to 800 DEG C.Finally take out Jiao and carry out survey sulphur, find that its desulfurization degree is 65.4%.
Embodiment 2
Get domestic certain Behavior of High-sulfur Petroleum Coke 3g, recording its sulphur content is 6.5wt.%, is crushed to 0.5 below mm, with the MoO being less than 0.1mm granularity
2be laid in the flat square porcelain boat of a 2 × 3cm after powder 0.0001g and the NiO powder 0.0002g being less than 0.1mm granularity fully mix.Then the porcelain boat containing burnt material is placed in stove, heats with the heating rate of 7 DEG C/Min, and pass into ammonia (in Reaktionsofen, ammonia pressure keeps 1 normal atmosphere), then at 700 DEG C of insulation 120min.Finally take out Jiao and carry out survey sulphur, find that its desulfurization degree is 79.9%.
Embodiment 3
Get domestic certain Behavior of High-sulfur Petroleum Coke 3g, recording its sulphur content is 6.5wt.%, is crushed to 0.5 below mm, with the MoO being less than 0.1mm granularity
2be laid in the flat square porcelain boat of a 2 × 3cm after powder 0.001g and the NiO powder 0.002g being less than 0.1mm granularity fully mix.Then the porcelain boat containing burnt material is placed in stove, heats with the heating rate of 7 DEG C/Min, and pass into ammonia (in Reaktionsofen, ammonia pressure keeps 1 normal atmosphere), then at 900 DEG C of insulation 120min.Finally take out Jiao and carry out survey sulphur, find that its desulfurization degree is 80.7%.
Embodiment 4
Get domestic certain Behavior of High-sulfur Petroleum Coke 3g, record its sulphur content 6.5wt.%, be crushed to 0.5 below mm, with the MoO being less than 0.1mm granularity
2be laid in the flat square porcelain boat of a 2 × 3cm after powder 0.01g and the NiO powder 0.02g being less than 0.1mm granularity fully mix.Then the porcelain boat containing burnt material is placed in stove, heats with the heating rate of 7 DEG C/Min, and pass into ammonia (in Reaktionsofen, ammonia pressure keeps 1 normal atmosphere), then at 800 DEG C of insulation 120min.Finally take out Jiao and carry out survey sulphur, find that its desulfurization degree is 83.5%.
Claims (6)
1. the method for a desulfurizing petrol coke, it is characterized in that: first refinery coke is broken into 1mm and following and mix with 0.1mm grade and following composite catalyst, the mass ratio of petroleum coke particles and composite catalyst is (10000-100): 1, and then pass into ammonia, be warming up to 700-900 DEG C simultaneously and be incubated 30-120min desulfurization; Described composite catalyst is NiO and MoO
2, NiO and MoO
2mass ratio is (4-2): 1.
2. method according to claim 1, is characterized in that: composite catalyst is that granularity is less than or equal to 0.075 mm.
3. method according to claim 1, is characterized in that: the ratio that petroleum coke particles mixes with composite catalyst is (5000-1000): 1.
4. method according to claim 1, is characterized in that: the granularity of refinery coke is less than or equal to 0.5mm.
5. the method for desulfurizing petrol coke according to claim 1, is characterized in that: described desulfurization temperature is 750-850 DEG C, and soaking time is 30-60 min.
6. the method for desulfurizing petrol coke according to claim 1, is characterized in that: ammonia pressure is more than or equal to 0.101MPa.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603216A (en) * | 2016-02-25 | 2016-05-25 | 沈阳北冶冶金科技有限公司 | Aluminum industry solid waste recovery/petroleum coke high-temperature desulphurization device and using method thereof |
| CN107384503A (en) * | 2017-08-09 | 2017-11-24 | 昆明理工大学 | A kind of sulfur method of petroleum coke |
| CN111675206A (en) * | 2020-05-29 | 2020-09-18 | 中南大学 | Desulfurization process of high-sulfur petroleum coke |
| CN115490227A (en) * | 2022-09-21 | 2022-12-20 | 湖南宸宇富基新能源科技有限公司 | Desulfurization-modification method of petroleum coke with medium and high sulfur content and method for preparing graphite cathode by desulfurization-modification method |
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| CN101015805A (en) * | 2007-02-07 | 2007-08-15 | 沈和平 | Catalyst for hydrorefining fraction oil and its prepn. |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105603216A (en) * | 2016-02-25 | 2016-05-25 | 沈阳北冶冶金科技有限公司 | Aluminum industry solid waste recovery/petroleum coke high-temperature desulphurization device and using method thereof |
| CN105603216B (en) * | 2016-02-25 | 2018-05-22 | 沈阳北冶冶金科技有限公司 | Aluminum i ndustry solid waste recycling/petroleum coke high temperature desulfurizing device and its application method |
| CN107384503A (en) * | 2017-08-09 | 2017-11-24 | 昆明理工大学 | A kind of sulfur method of petroleum coke |
| CN111675206A (en) * | 2020-05-29 | 2020-09-18 | 中南大学 | Desulfurization process of high-sulfur petroleum coke |
| CN111675206B (en) * | 2020-05-29 | 2021-09-03 | 中南大学 | Desulfurization process of high-sulfur petroleum coke |
| CN115490227A (en) * | 2022-09-21 | 2022-12-20 | 湖南宸宇富基新能源科技有限公司 | Desulfurization-modification method of petroleum coke with medium and high sulfur content and method for preparing graphite cathode by desulfurization-modification method |
| CN115490227B (en) * | 2022-09-21 | 2024-02-09 | 湖南宸宇富基新能源科技有限公司 | Desulfurization-modification method for medium-high sulfur petroleum coke and preparation method and application of desulfurization-modification method for medium-high sulfur petroleum coke to graphite negative electrode |
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Application publication date: 20151028 |