CN105062612A - Method for desulfurization of petroleum coke - Google Patents
Method for desulfurization of petroleum coke Download PDFInfo
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- CN105062612A CN105062612A CN201510451291.0A CN201510451291A CN105062612A CN 105062612 A CN105062612 A CN 105062612A CN 201510451291 A CN201510451291 A CN 201510451291A CN 105062612 A CN105062612 A CN 105062612A
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- coke
- desulfurization
- petroleum coke
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Abstract
The invention discloses a method for desulfurization of petroleum coke. The method comprises the steps: under an ammonia atmosphere, mixing petroleum coke and a trace catalyst and heating to 700-900 DEG C, and carrying out heat preservation, so as to achieve the purpose of desulfurization, wherein the mass ratio of petroleum coke particles to the composite catalyst is (10000-100) to 1; and then introducing ammonia gas, simultaneously heating up to 700-900 DEG C, carrying out heat preservation for 30-120 min, and desulfurizing, wherein the composite catalyst comprises NiS, MoS2 and CoS with the particle size of less than or equal to 0.1 mm, and the mass ratio of NiS to MoS2 to CoS is 1 to (0.3-0.5) to (0.1-0.2). In the case without consuming more heat energy and affecting the performance of the petroleum coke, the effect of ammonia gas atmosphere desulfurization is further improved by 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 CN104611087A 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 CN103555389A 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 CN101020854A 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 CN101804977A 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 CN101144044A 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 CN104129774A 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 method 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%.
Detailed 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 the NiS adopting granularity to be less than or equal to 0.1mm, MoS
2and CoS, NiS, MoS
2be 1:(0.3-0.5 with CoS mass ratio): (0.1-0.2).
Further, wherein composite catalyst is that granularity is less than or equal to 0.075mm.
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 30-60min.
Further, wherein ammonia pressure is more than or equal to 0.101MPa.
Further, the sulfide of nickel, molybdenum and cobalt 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 sulfide of mixed Ni, molybdenum and cobalt element is studied discovery through us and finally can be formed one and can be expressed as CoMo
1.5ni
xs
x+4(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 1:(0.3-0.5 on a series of experiment basis): (0.1-0.2) 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 sulfide 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 high sulfur petroleum coke 15g, recording its sulphur content is 6.5wt%, is crushed to below 1mm, with the MoS being less than 0.075mm granularity
2powder 0.0003g, the CoS powder 0.0002g being less than 0.075mm granularity and the NiS powder 0.001g being less than 0.075mm granularity fully mix, and are then laid in the flat square porcelain boat of a 2 × 3cm.Again sample is placed in atmosphere furnace to carry out adding thermally desulfurizing.Add thermally desulfurizing process experiment condition: atmosphere furnace is warming up to 800 DEG C with 7 DEG C/Min temperature rise rate, 800 DEG C of insulations 2 hours.Ammonia (in Reaktionsofen, ammonia pressure keeps 1 normal atmosphere) is just passed into when heating and starting.Finally take out sample to weigh, the actual mass obtaining refinery coke after deducting the quality of the metal catalyst be mixed into surveys sulphur again, and find that sulphur content is down to 1.23wt%, desulfurization degree is 81.08%.With comparative example 1,2, in 3, to compare the promotion sweetening effectiveness of composite catalyst better in the catalysis of single sulfide.As shown in table 1 in addition, change CoS, MoS under the same conditions as example 1
2with the proportioning of NiS by experiment and XRD reach a conclusion, at NiS, MoS after detecting
2be 1:(0.3-0.5 with CoS mass ratio): more easily form CoMo in the scope of (0.1-0.2)
1.5ni
xs
x+4compound, and reach higher sweetening effectiveness.After mass ratio goes beyond the scope, 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
| NiS、MoS 2With the proportioning of CoS | Desulfurization degree (%) |
| 1：0.1：0.1 | 73.4 |
| 1：0.2：0.2 | 75.9 |
| 1：0.3：0.3 | 76.8 |
| 1：0.3：0.2 | 81.1 |
| 1：0.4：0.4 | 76.9 |
| 1：0.4：0.3 | 78.3 |
| 1：0.4：0.2 | 82.4 |
| 1：0.5：0.5 | 75.1 |
| 1：0.5：0.4 | 77.0 |
| 1：0.5：0.3 | 79.8 |
| 1：0.5：0.2 | 82.7 |
Comparative example 1
Get domestic certain high sulfur petroleum coke 15g, recording its sulphur content is 6.5wt%, is crushed to below 1mm, fully mixes, be then laid in the flat square porcelain boat of a 2 × 3cm with the NiS powder 0.0015g being less than 0.075mm granularity.Again sample is placed in atmosphere furnace to carry out adding thermally desulfurizing.Add thermally desulfurizing process experiment condition: atmosphere furnace is warming up to 800 DEG C with 7 DEG C/Min temperature rise rate, 800 DEG C of insulations 2 hours.Ammonia (in Reaktionsofen, ammonia pressure keeps 1 normal atmosphere) is just passed into when heating and starting.Finally take out sample to weigh, the actual mass obtaining refinery coke after deducting the quality of the metal catalyst be mixed into surveys sulphur again, finds that desulfurization degree is 69.70%.
Comparative example 2
Get domestic certain high sulfur petroleum coke 15g, recording its sulphur content is 6.5wt%, is crushed to below 1mm, fully mixes, be then laid in the flat square porcelain boat of a 2 × 3cm with the CoS powder 0.0015g being less than 0.075mm granularity.Again sample is placed in atmosphere furnace to carry out adding thermally desulfurizing.Add thermally desulfurizing process experiment condition: atmosphere furnace is warming up to 800 DEG C with 7 DEG C/Min temperature rise rate, 800 DEG C of insulations 2 hours.Ammonia (in Reaktionsofen, ammonia pressure keeps 1 normal atmosphere) is just passed into when heating and starting.Finally take out sample to weigh, the actual mass obtaining refinery coke after deducting the quality of the metal catalyst be mixed into surveys sulphur again, finds that desulfurization degree is 70.1%.
Comparative example 3
Get domestic certain high sulfur petroleum coke 15g, recording its sulphur content is 6.5wt%, is crushed to below 1mm, with the MoS being less than 0.075mm granularity
2powder 0.0015g fully mixes, and is then laid in the flat square porcelain boat of a 2 × 3cm.Again sample is placed in atmosphere furnace to carry out adding thermally desulfurizing.Add thermally desulfurizing process experiment condition: atmosphere furnace is warming up to 800 DEG C with 7 DEG C/Min temperature rise rate, 800 DEG C of insulations 2 hours.Ammonia (in Reaktionsofen, ammonia pressure keeps 1 normal atmosphere) is just passed into when heating and starting.Finally take out sample to weigh, the actual mass obtaining refinery coke after deducting the quality of the metal catalyst be mixed into surveys sulphur again, finds that desulfurization degree is 69.8%.
Embodiment 2
Get domestic certain high sulfur petroleum coke 15g, recording its sulphur content is 6.5wt%, is crushed to below 1mm, with the MoS being less than 0.1mm granularity
2powder 0.0003g, the CoS powder 0.0002g being less than 0.1mm granularity and the NiS powder 0.001g being less than 0.1mm granularity fully mix, and are then laid in the flat square porcelain boat of a 2 × 3cm.Again sample is placed in atmosphere furnace to carry out adding thermally desulfurizing.Add thermally desulfurizing process experiment condition: atmosphere furnace is warming up to 800 DEG C with 7 DEG C/Min temperature rise rate, 800 DEG C of insulations 2 hours.Ammonia (in Reaktionsofen, ammonia pressure keeps 1 normal atmosphere) is just passed into when heating and starting.Finally take out sample to weigh, the actual mass obtaining refinery coke after deducting the quality of the metal catalyst be mixed into surveys sulphur again, finds that desulfurization degree is 80.52%.
Embodiment 3
Get domestic certain high sulfur petroleum coke 15g, recording its sulphur content is 6.5wt%, is crushed to below 1mm, with the MoS being less than 0.1mm granularity
2powder 0.003g, the CoS powder 0.002g being less than 0.1mm granularity and the NiS powder 0.01g being less than 0.1mm granularity fully mix, and are then laid in the flat square porcelain boat of a 2 × 3cm.Again sample is placed in atmosphere furnace to carry out adding thermally desulfurizing.Add thermally desulfurizing process experiment condition: atmosphere furnace is warming up to 800 DEG C with 7 DEG C/Min temperature rise rate, 800 DEG C of insulations 2 hours.Ammonia (in Reaktionsofen, ammonia pressure keeps 1 normal atmosphere) is just passed into when heating and starting.Finally take out sample to weigh, the actual mass obtaining refinery coke after deducting the quality of the metal catalyst be mixed into surveys sulphur again, finds that desulfurization degree is 82.50%.
Embodiment 4
Get domestic certain high sulfur petroleum coke 15g, recording its sulphur content is 6.5wt%, is crushed to below 1mm, with the MoS being less than 0.1mm granularity
2powder 0.03g, the CoS powder 0.02g being less than 0.1mm granularity and the NiS powder 0.1g being less than 0.1mm granularity fully mix, and are then laid in the flat square porcelain boat of a 2 × 3cm.Again sample is placed in atmosphere furnace to carry out adding thermally desulfurizing.Add thermally desulfurizing process experiment condition: atmosphere furnace is warming up to 800 DEG C with 7 DEG C/Min temperature rise rate, 800 DEG C of insulations 2 hours.Ammonia (in Reaktionsofen, ammonia pressure keeps 1 normal atmosphere) is just passed into when heating and starting.Finally take out sample to weigh, the actual mass obtaining refinery coke after deducting the quality of the metal catalyst be mixed into surveys sulphur again, finds that desulfurization degree is 84.71%.
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 the NiS adopting granularity to be less than or equal to 0.1mm, MoS
2and CoS, NiS, MoS
2be 1:(0.3-0.5 with CoS mass ratio): (0.1-0.2).
2. the method for desulfurizing petrol coke according to claim 1, is characterized in that: the granularity of composite catalyst is less than or equal to 0.075mm.
3. the method for desulfurizing petrol coke according to claim 1, is characterized in that: the mass ratio of petroleum coke particles and composite catalyst is (5000-1000): 1.
4. the method for desulfurizing petrol coke 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 30-60min.
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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108641776A (en) * | 2018-04-27 | 2018-10-12 | 昆明理工大学 | A method of removing sulfur in petroleum coke with manganese powder |
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2015
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108641776A (en) * | 2018-04-27 | 2018-10-12 | 昆明理工大学 | A method of removing sulfur in petroleum coke with manganese powder |
| CN108641776B (en) * | 2018-04-27 | 2020-11-17 | 昆明理工大学 | Method for removing sulfur in petroleum coke by using manganese powder |
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