CN105036113B - A kind of method of desulfurizing petrol coke - Google Patents
A kind of method of desulfurizing petrol coke Download PDFInfo
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- CN105036113B CN105036113B CN201510451270.9A CN201510451270A CN105036113B CN 105036113 B CN105036113 B CN 105036113B CN 201510451270 A CN201510451270 A CN 201510451270A CN 105036113 B CN105036113 B CN 105036113B
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- petroleum coke
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Abstract
The invention discloses a kind of methods of desulfurizing petrol coke.Petroleum coke and trace catalyst are carried out between being mixed and heated to 700 900 DEG C degrees Celsius under ammonia atmosphere, and kept the temperature, to reach desulfurization purpose, the mass ratio of petroleum coke particles and composite catalyst is（10000‑100）：1, it is then passed through ammonia again, while being warming up to 700 900 DEG C and keeping the temperature 30 120min desulfurization；The composite catalyst is the NiS, MoS for being less than or equal to 0.1 mm using granularity2And CoS, NiS, MoS2It is 1 with CoS mass ratioes：（0.3‑0.5）：（0.1‑0.2）.The present invention passes through the means for adding trace catalyst so that the effect of ammonia atmosphere desulfurization further increases in the case where not expending more thermal energy not and influencing petroleum coke performance.
Description
Technical field
The present invention relates to a kind of methods of desulfurizing petrol coke, are applied to metallurgy, material, chemical industry and environmental technology field.
Background technology
Petroleum coke is the principal by product of oil refining industry, is generally made by delay coking process.Petroleum coke is because having
Ash content is low, and the features such as fixed carbon content height are widely used in the fields such as metallurgical, material and chemical industry.Meanwhile because of sulfur in petroleum coke
Content is different, and petroleum coke is divided into high-sulfur（>4%）, middle sulphur（2-4%）With low-sulfur coke（<2%）.But with the deterioration of international crude petroleum and
Acidification, the quality of the petroleum coke of the byproduct as oil refining are also continuously decreasing, and especially the sulfur content in petroleum coke exists
It is continuously improved.The quality of sulphur content too high levels meeting strong influence product in petroleum coke.At the same time, in petroleum coke
Sulphur content increases, and also carries the ring of more and more arduous control sulphur emissions accordingly using petroleum coke as the industrial enterprise of subordinate of raw material
Packing pressure.
For carbon anode being prepared using petroleum coke as raw material.Sulphur in petroleum coke is mainly deposited with thiophene-based aromatic hydrocarbon material
It can not removed from petroleum coke under normal calcination temperature.In anode preparation process, in order to effectively remove sulphur content,
It can only solve the problems, such as that sulfur content is excessively high to improve the calcination temperature of petroleum coke.Therefore, the sulphur in limited reduction Behavior of High-sulfur Petroleum Coke
While content, high-temperature calcination not only improves the economic cost of calcining, the calcined coke also reduced to a certain extent it is paid
Rate improves the anode manufacturing cost of enterprise, affects economic benefit.
In addition, high sulfur petroleum coke can only be used simply as fuel because of the high characteristic of its sulfur content.With oil
Coke is high-quality low-sulfur petroleum coke under the very fast development of carbon industry and the higher and higher industry background of raw petroleum coke sulfur content of raw material
Production capacity notch it is increasing.Therefore, how environmental protection, efficient become current carbon industry using high sulfur petroleum coke inferior and compel
Cut problem to be solved.
Patent Application Publication CN 104611087A are not directed to using the sulphur in ammonia calcination method removing petroleum coke
The addition and use of catalyst.
The method that 103555389 A of Patent Application Publication CN refer to a kind of desulfurization of petroleum coke while avoiding coking.But
It uses method for solid fuel particle, quartzy sandstone and lime stone, burns in high-velocity fluidized bed.Although controlled at 850
~900 DEG C, but operating process needs that quartzy sandstone and lime stone is added.
101020854 A of patent CN refer to a kind of petroleum coke gasification hydrogen-producing desulfurization coupling scheme.But use method for
Petroleum coke and sodium carbonate or potassium carbonate are mixed, reactor is added, and is passed through steam gasification.And to oil after gasification reaction
Coke carries out pickling, washing and drying.
101804977 A of patent CN refer to the sulphur content technology in a kind of acid system removing petroleum coke.Method is normal
Petroleum coke fine grained is placed in certain time in mixed acid desulfurizing agent at 0-60 DEG C by pressure, and then petroleum coke is isolated and washed again
It washs.
101144044 A of patent CN are utilized in the one kind being added in petroleum coke in vulcanization zirconium, cerium sulphide and yttrium sulfide
Desulfurizing agent is calcined, and calcination temperature is used and carried out at 1270-1500 DEG C.
104129774 A of patent CN provide a kind of desulfurization technology.Method be under the premise of petroleum coke is broken according to
Mischmetal and nitric acid-hydrochloric acid-hydrogen peroxide desulfurizing agent is added in certain mixing ratio, then remixes uniformly and is stirred.Again
By separation, 1300-1350 DEG C of calcining finally obtains the petroleum coke product of low sulfur content.
Invention content
A kind of method the purpose of the present invention is removing sulfur in petroleum coke for ammonia pyrogenic process, it is proposed that significantly more efficient rush
Into the method for desulfuration efficiency, desulfurization degree can be more than 80%.
Detailed process is as follows：First by petroleum coke be broken into 1mm and it is following and with 0.1mm grades and composite catalyst below
It mixes, the mass ratio of petroleum coke particles and composite catalyst is（10000-100）：1, it is then passed through ammonia again, is warming up to simultaneously
700-900 DEG C and keep the temperature 30-120min desulfurization；The composite catalyst is the NiS for being less than or equal to 0.1 mm using granularity,
MoS2And CoS, NiS, MoS2It is 1 with CoS mass ratioes：（0.3-0.5）：（0.1-0.2）.
Further, wherein composite catalyst is that granularity is less than or equal to 0.075 mm.
Further, wherein petroleum coke particles and the ratio of composite catalyst mixing are（5000-1000）：1.
Further, wherein the granularity of petroleum coke is less than or equal to 0.5mm.
Further, wherein the desulfurization temperature is 750-850 DEG C, soaking time is 30-60 min.
Further, wherein ammonia pressure is more than or equal to 0.101MPa.
Further, the sulfide of nickel, molybdenum and cobalt element can promote the principle sheet that ammonia is reacted with sulfur in petroleum coke point
Under the conditions of matter is existing for this variable valency metal and its compound, sulphur content is more prone to take off from the organic compounds such as thiophene
From, with ammonia generate active hydrogen atom react generation H2S and remove in petroleum coke.But in desulfurizing petrol coke, single member
The catalytic effect of element is simultaneously bad, on the contrary, the sulfide of mixed Ni, molybdenum and cobalt element is through me under about 600 DEG C or more ammonia atmospheres
Study discovery and may eventually form one kind and can be expressed as CoMo1.5NixSx+4（x>1）The porous high surface area material of complexity, should
1+1 can be presented to the desulfurizing petrol coke under ammonia atmosphere in substance>2 effect.In order to be calcined in sweetening process under ammonia atmosphere
This catalyst is converted to the greatest extent to reach so as to optimal desulfurization effect, we determine on a series of experiment basis
1：（0.3-0.5）：（0.1-0.2）This proportioning.
The outstanding feature of the present invention：
1 present invention can further be greatly reduced in Behavior of High-sulfur Petroleum Coke compared with simple ammonia desulfurization at a lower temperature
Sulfur content so that the sulphur in petroleum coke can focus on, that is, mitigate charcoal element and produce the environmental protection pressure of follow-up workshop section, and can be with
The sulphur of removing is made into sulfur-bearing chemicals.
2 present invention can effectively improve the utilization rate of high sulfur petroleum coke.Further having expanded the raw material of carbon industry makes
Use range.
The metal sulfide catalyst additive amount used in 3 present invention is few, cheap.
4 implementing process of the present invention are simple and convenient, can remove sulphur in the normal calcination process of raw material.
Petroleum coke microstructure and former coke after 5 inventive desulfurizations is essentially identical, and the addition of this kind of metallic catalyst is not right
Burnt surface texture damages.
Specific implementation mode
It is described further with reference to specific embodiment, but the present invention is not therefore subject to any restriction.
Embodiment 1
Take domestic certain high sulfur petroleum coke 15g, it is 6.5wt% to measure its sulfur content, be crushed to 1 mm hereinafter, with less than
The MoS of 0.075mm granularities2Powder 0.0003g, less than the CoS powder 0.0002g of 0.075mm granularities and less than 0.075mm granularities
NiS powder 0.001g is sufficiently mixed, and is then laid in the flat rectangular porcelain boat of a 2 × 3cm.Sample is placed in atmosphere furnace again
Carry out heating desulfurization.Heat desulfurization process experiment condition：Atmosphere furnace is warming up to 800 DEG C with 7 DEG C/Min heating rates, at 800 DEG C
Heat preservation 2 hours.It is just passed through ammonia at the beginning of heating（Ammonia pressure keeps 1 atmospheric pressure in reacting furnace）.Finally take out sample
It is weighed, subtracts and obtain the actual mass of petroleum coke after the quality of mixed metallic catalyst and survey sulphur again, found sulfur content
Through being down to 1.23wt%, desulfurization degree 81.08%.Catalytic phase with single sulfide in comparative example 1,2,3 is than composite catalyst
Promote desulfurization effect more preferable.In addition as shown in table 1, change CoS, MoS under the same conditions as example 12With the proportioning of NiS
By drawing a conclusion after experiment and XRD detections, in NiS, MoS2It is 1 with CoS mass ratioes：（0.3-0.5）：（0.1-0.2）Model
It is easier to form CoMo in enclosing1.5NixSx+4Compound, and reach higher desulfurization effect.After mass ratio goes beyond the scope, due to
The compound of catalyst wherein main function under phase homogenous quantities forms less, and effect is affected instead.
Table 1
| NiS、MoS2With 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
Take domestic certain high sulfur petroleum coke 15g, it is 6.5wt% to measure its sulfur content, be crushed to 1 mm hereinafter, with less than
The NiS powder 0.0015g of 0.075mm granularities is sufficiently mixed, and is then laid in the flat rectangular porcelain boat of a 2 × 3cm.Again by sample
Product, which are placed in atmosphere furnace, carries out heating desulfurization.Heat desulfurization process experiment condition：Atmosphere furnace is warming up to 7 DEG C/Min heating rates
800 DEG C, 2 hours are kept the temperature at 800 DEG C.It is just passed through ammonia at the beginning of heating（Ammonia pressure keeps 1 atmospheric pressure in reacting furnace）.
It finally takes out sample to be weighed, subtracts and obtain the actual mass of petroleum coke after the quality of mixed metallic catalyst and survey sulphur again,
It was found that desulfurization degree is 69.70%.
Comparative example 2
Take domestic certain high sulfur petroleum coke 15g, it is 6.5wt% to measure its sulfur content, be crushed to 1 mm hereinafter, with less than
The CoS powder 0.0015g of 0.075mm granularities is sufficiently mixed, and is then laid in the flat rectangular porcelain boat of a 2 × 3cm.Again by sample
Product, which are placed in atmosphere furnace, carries out heating desulfurization.Heat desulfurization process experiment condition：Atmosphere furnace is warming up to 7 DEG C/Min heating rates
800 DEG C, 2 hours are kept the temperature at 800 DEG C.It is just passed through ammonia at the beginning of heating（Ammonia pressure keeps 1 atmospheric pressure in reacting furnace）.
It finally takes out sample to be weighed, subtracts and obtain the actual mass of petroleum coke after the quality of mixed metallic catalyst and survey sulphur again,
It was found that desulfurization degree is 70.1%.
Comparative example 3
Take domestic certain high sulfur petroleum coke 15g, it is 6.5wt% to measure its sulfur content, be crushed to 1 mm hereinafter, with less than
The MoS of 0.075mm granularities2Powder 0.0015g is sufficiently mixed, and is then laid in the flat rectangular porcelain boat of a 2 × 3cm.Again will
Sample, which is placed in atmosphere furnace, carries out heating desulfurization.Heat desulfurization process experiment condition：Atmosphere furnace is heated up with 7 DEG C/Min heating rates
To 800 DEG C, 2 hours are kept the temperature at 800 DEG C.It is just passed through ammonia at the beginning of heating（Ammonia pressure keeps 1 air in reacting furnace
Pressure）.It finally takes out sample to be weighed, subtracts and obtain the actual mass of petroleum coke after the quality of mixed metallic catalyst and survey again
Sulphur finds that desulfurization degree is 69.8%.
Embodiment 2
Take domestic certain high sulfur petroleum coke 15g, it is 6.5wt% to measure its sulfur content, be crushed to 1 mm hereinafter, with less than
The MoS of 0.1 mm granularities2Powder 0.0003g, the CoS powder 0.0002g less than 0.1 mm granularities and the NiS powder less than 0.1 mm granularities
0.001g is sufficiently mixed, and is then laid in the flat rectangular porcelain boat of a 2 × 3cm.Sample is placed in atmosphere furnace again and is carried out
Heat desulfurization.Heat desulfurization process experiment condition：Atmosphere furnace is warming up to 800 DEG C with 7 DEG C/Min heating rates, and 2 are kept the temperature at 800 DEG C
Hour.It is just passed through ammonia at the beginning of heating（Ammonia pressure keeps 1 atmospheric pressure in reacting furnace）.Sample is finally taken out to be claimed
Amount subtracts and obtains the actual mass of petroleum coke after the quality of mixed metallic catalyst and survey sulphur again, it is found that desulfurization degree is 80.52%.
Embodiment 3
Take domestic certain high sulfur petroleum coke 15g, it is 6.5wt% to measure its sulfur content, be crushed to 1 mm hereinafter, with less than
The MoS of 0.1 mm granularities2Powder 0.003g, the CoS powder 0.002g less than 0.1 mm granularities and the NiS powder less than 0.1 mm granularities
0.01g is sufficiently mixed, and is then laid in the flat rectangular porcelain boat of a 2 × 3cm.Sample is placed in atmosphere furnace again and is added
Thermally desulfurizing.Heat desulfurization process experiment condition：Atmosphere furnace is warming up to 800 DEG C with 7 DEG C/Min heating rates, and it is small that 2 are kept the temperature at 800 DEG C
When.It is just passed through ammonia at the beginning of heating（Ammonia pressure keeps 1 atmospheric pressure in reacting furnace）.Sample is finally taken out to be claimed
Amount subtracts and obtains the actual mass of petroleum coke after the quality of mixed metallic catalyst and survey sulphur again, it is found that desulfurization degree is 82.50%.
Embodiment 4
Take domestic certain high sulfur petroleum coke 15g, it is 6.5wt% to measure its sulfur content, be crushed to 1 mm hereinafter, with less than
The MoS of 0.1 mm granularities2Powder 0.03g, the CoS powder 0.02g less than 0.1 mm granularities and the NiS powder 0.1g less than 0.1 mm granularities
It is sufficiently mixed, is then laid in the flat rectangular porcelain boat of a 2 × 3cm.Sample is placed in atmosphere furnace again heat and is taken off
Sulphur.Heat desulfurization process experiment condition：Atmosphere furnace is warming up to 800 DEG C with 7 DEG C/Min heating rates, and 2 hours are kept the temperature at 800 DEG C.
It is just passed through ammonia at the beginning of heating（Ammonia pressure keeps 1 atmospheric pressure in reacting furnace）.It finally takes out sample to be weighed, subtract
It goes after the quality of mixed metallic catalyst the actual mass for obtaining petroleum coke to survey sulphur again, it is found that desulfurization degree is 84.71%.
Claims (6)
1. a kind of method of desulfurizing petrol coke, it is characterised in that：First by petroleum coke be broken into 1mm or less and with 0.1mm grades with
Under composite catalyst mixing, the mass ratio of petroleum coke particles and composite catalyst is（10000-100）：1, it is then passed through ammonia again
Gas, while being warming up to 700-900 DEG C and keeping the temperature 30-120min desulfurization；The composite catalyst is less than or is waited using granularity
In the NiS of 0.1 mm, MoS2And CoS, NiS, MoS2It is 1 with CoS mass ratioes：（0.3-0.5）：（0.1-0.2）.
2. according to the method described in claim 1, it is characterized in that：Catalyst is that granularity is less than or equal to 0.075 mm.
3. according to the method described in claim 1, it is characterized in that：Petroleum coke particles and the ratio of catalyst mixing are（5000-
1000）：1.
4. according to the method described in claim 1, it is characterized in that：The granularity of petroleum coke is less than or equal to 0.5mm.
5. the method for desulfurizing petrol coke according to claim 1, it is characterised in that：The desulfurization temperature is 750-850
DEG C, soaking time is 30-60 min.
6. the method for desulfurizing petrol coke according to claim 1, it is characterised in that：Ammonia pressure is more than or equal to
0.101MPa。
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| CN104611087A (en) * | 2015-03-10 | 2015-05-13 | 中南大学 | Petroleum coke desulfurizing method |
| CN104650965A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Method for catalyzing gasoline deep desulfurization with Ni-Mo-Co containing catalyst |
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| CN104650965A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Method for catalyzing gasoline deep desulfurization with Ni-Mo-Co containing catalyst |
| CN104611087A (en) * | 2015-03-10 | 2015-05-13 | 中南大学 | Petroleum coke desulfurizing method |
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