CN109797002A - A kind of steel scrap ROLLING OIL recycling processing method - Google Patents

A kind of steel scrap ROLLING OIL recycling processing method Download PDF

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Publication number
CN109797002A
CN109797002A CN201910083336.1A CN201910083336A CN109797002A CN 109797002 A CN109797002 A CN 109797002A CN 201910083336 A CN201910083336 A CN 201910083336A CN 109797002 A CN109797002 A CN 109797002A
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China
Prior art keywords
rolling oil
steel scrap
reaction
scrap rolling
solid
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CN201910083336.1A
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Chinese (zh)
Inventor
夏明桂
周玉清
夏王哲
方派
何秋瑾
王彩凤
夏广
王�琦
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Wuhan Textile University
Original Assignee
ANHUI GUOFU LUBRICANT INDUSTRY Co Ltd
Hubei Australian Rare Source Technology Co Ltd
Wuhan Textile University
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Priority to CN201910083336.1A priority Critical patent/CN109797002A/en
Publication of CN109797002A publication Critical patent/CN109797002A/en
Pending legal-status Critical Current

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Abstract

The present invention relates to the process fields of steel scrap ROLLING OIL, disclose a kind of steel scrap ROLLING OIL recycling processing method, characterized by comprising the following steps: (1) in the presence of the catalysts and solvents of optional addition, makes steel scrap ROLLING OIL carry out hydrogenation reaction in hydrogen atmosphere;(2) mixture after reaction is separated by solid-liquid separation, the liquid phase isolated is distilled, gasoline and diesel oil distillate are obtained.It is method economical and effective of the present invention, simple and easy to do, dangerous waste steel scrap ROLLING OIL can be turned waste into wealth, both can produce economic benefit, can also generate social benefit.

Description

A kind of steel scrap ROLLING OIL recycling processing method
Technical field
The present invention relates to the process fields of steel scrap ROLLING OIL, and in particular to a kind of steel scrap ROLLING OIL recycling processing method.
Background technique
ROLLING OIL is widely used in metallurgical industry, the annual whole nation has a large amount of waste rolling oil to generate.It gives up and rolls for many years The Utilizing question of liquefaction is always a great problem for perplexing enterprise.Most of enterprise burns up or works as using waste rolling oil as fuel oil Waste oil is sold, and environment is not only polluted, and causes the significant wastage of resource.
The characteristics of there are many waste rolling oil classification, there is aluminium scrap ROLLING OIL, steel scrap ROLLING OIL etc., steel scrap ROLLING OIL are that solid iron contains Amount is high, and aqueous, surfactant, oleic acid, grease even mineral oil etc., separating difficulty is big, iron particle granularity especially therein Between dozens to a few hundred nanometers, use conventional methods such as filter, the means of centrifugation can only be completed in laboratory, and time Long, fractional dose is small, cannot achieve industrial separation, causes steel scrap ROLLING OIL that can only be burned as dangerous waste.But steel scrap rolls Containing a large amount of unmetamorphosed effective component in oil, if iron powder mass content reaches 95% or more in solid phase, in oily phase effectively at Point mass content reaches 90% or more, burns the huge waste for causing resource.
Chinese patent application CN105754706A, CN101665741A discloses the method for two kinds of regeneration waste rolling oils, point Alkali plus flocculated method Cai Yong not added to handle waste rolling oil, but the very low lotion of solid content can only be handled, existed for solid content The steel scrap ROLLING OIL of the semi-solid state of 10-40% does not have separating effect.For current technical deficiency, the invention patent is by dangerous waste Steel scrap ROLLING OIL carry out recycling treatment, convert industrial chemicals for iron powder in solid phase therein, by oily inversion of phases be lotion Dangerous waste steel scrap ROLLING OIL is turned waste into wealth, both can produce economic benefit, can also generate social benefit by raw material.
Summary of the invention
The method of existing processing steel scrap ROLLING OIL can only handle the very low lotion of solid content, for solid content in 10- The steel scrap ROLLING OIL of 40% semi-solid state does not have separating effect.For the deficiency of current technology, it is logical that the present invention provides one kind It crosses and steel scrap ROLLING OIL is carried out adding hydrogen to realize the method for recycling steel scrap ROLLING OIL.In method of the present invention, lead to Hydrogenation reaction is crossed, so that the viscosity of steel scrap ROLLING OIL substantially reduces, is passed through so that being difficult to isolated nano grade iron powder originally Simple be separated by solid-liquid separation can separate, and the solid phase after separation of solid and liquid contains a large amount of iron powder, can be used as catalytic agent reuse In hydrogenation process, industrial chemicals can also be used as;Liquid phase after separation of solid and liquid can obtain gasoline and bavin by rectifying Oil distillate realizes turning waste into wealth for dangerous waste steel scrap ROLLING OIL.
To achieve the goals above, one aspect of the present invention provides a kind of steel scrap ROLLING OIL recycling processing method, including with Lower step:
(1) in the presence of the catalysts and solvents of optional addition, steel scrap ROLLING OIL is made to carry out adding hydrogen in hydrogen atmosphere Reaction;
(2) mixture after reaction is separated by solid-liquid separation, the liquid phase isolated is distilled, gasoline and diesel oil are obtained Fraction.
Preferably, in the hydrogenation process described in step (1), hydrogen partial pressure 2-15MPa.
Preferably, in the hydrogenation process described in step (1), reaction temperature is 250-370 DEG C.
Preferably, the dosage of the catalyst is the 0-10% of the steel scrap ROLLING OIL weight.
Preferably, solvent described in step (1) is at least one of toluene, benzene, methanol and ethyl acetate.
Preferably, the dosage of the solvent is the 0-200% of the steel scrap ROLLING OIL weight.
Preferably, described to be separated by solid-liquid separation as filtering or centrifuge separation in step (2).
Preferably, the method also includes: the solid phase isolated in separation of solid and liquid process is back to described in step (1) In hydrogenation reaction.
Through the above technical solutions, can effectively isolate nanoscale iron particle in steel scrap ROLLING OIL, and pass through Gasoline and diesel oil distillate can be obtained by carrying out rectifying to the liquid phase isolated, to realize at the recycling of steel scrap ROLLING OIL Reason.
Moreover, method of the present invention is not limited by solid content in steel scrap ROLLING OIL, it is easy to operate, it is easy to accomplish Industrialization.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
To achieve the goals above, the present invention provides a kind of steel scrap ROLLING OIL recycling processing method, comprising the following steps:
(1) in the presence of the catalysts and solvents of optional addition, steel scrap ROLLING OIL is made to carry out adding hydrogen in hydrogen atmosphere Reaction;
(2) mixture after reaction is separated by solid-liquid separation, the liquid phase isolated is distilled, gasoline and diesel oil are obtained Fraction.
In the preferred embodiment of the present invention, in the hydrogenation process described in step (1), hydrogen partial pressure 2- 15MPa, it is highly preferred that hydrogen partial pressure be 3-12MPa, such as can for 3MPa, 3.5MPa, 4MPa, 5MPa, 6MPa, 8MPa, 10MPa or 12MPa.
In the preferred embodiment of the present invention, in the hydrogenation process described in step (1), reaction temperature 250- 370 DEG C, for example, can for 250 DEG C, 260 DEG C, 270 DEG C, 280 DEG C, 290 DEG C, 300 DEG C, 310 DEG C, 320 DEG C, 330 DEG C, 340 DEG C, 350 DEG C, 360 DEG C or 370 DEG C.
In method of the present invention, the reactive mode of hydrogenation reaction described in step (1) can for fixed bed reaction, Fluidized-bed reaction, slurry reactor or autoclave intermittent reaction.In a specific embodiment, when the hydrogenation reaction is autoclave When intermittent reaction, the reaction time of hydrogenation reaction is 30min to 10h, preferably 1-5h.
Catalyst can not additionally be added in method of the present invention, during the hydrogenation reaction (i.e. plus hydrogen Catalyst), catalyst can also additionally be added.In a particular embodiment, volume is not needed during the hydrogenation reaction Outer addition catalyst, because the iron (nano-scale) in steel scrap ROLLING OIL can play the role of catalyst.
In interchangeable embodiment, catalyst is additionally added during the hydrogenation reaction.The catalyst can Think hydrogenation catalyst commonly used in the art.The hydrogenation catalyst can for metallic catalyst (such as Ni, Mo, Co, Pd or Pt);It may be loaded catalyst, if metal active constituent is carried on the inorganic supported type metallic catalyst of inorganic carrier, Wherein, metal active constituent can be Ni, Mo, Co, Pd or Pt, and inorganic carrier can be Al2O3、SiO2, porous ceramics, activity Charcoal or molecular sieve, in a specific embodiment, the loaded catalyst are Mo2C/ beta-zeolite catalyst.
In interchangeable embodiment, when catalyst additionally is added during the hydrogenation reaction, the catalysis The dosage of agent is the 0%-10% of the steel scrap ROLLING OIL weight, specifically, such as can for 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, 4%, 6%, 8% or 10%.
In method of the present invention, solvent can not additionally be added during the hydrogenation reaction, it can also be with volume Outer addition solvent.The solvent is the conventional selection of this field, such as can be in toluene, benzene, methanol or ethyl acetate At least one.In interchangeable embodiment, when solvent additionally is added during the hydrogenation reaction, the solvent Dosage be steel scrap ROLLING OIL weight 0-200%, it is highly preferred that the dosage of solvent be steel scrap roll oil quality 0-100%, Specifically, for example, can for steel scrap ROLLING OIL 0.1%, 0.5%, 1%, 2%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100%.
In method of the present invention, in step (2), the separation of solid and liquid can be filtering or centrifuge separation.Institute State centrifuge separation operating condition may include: revolving speed be 2000-10000rpm (specifically, for example, can be 2000rpm, 3000rpm, 4000rpm, 5000rpm, 6000rpm, 7000rpm, 8000rpm, 9000rpm or 10000rpm), when centrifuge separation Between can be 1min-60min (specifically, for example, can be 1min, 2min, 4min, 6min, 8min, 10min, 20min, 30min, 40min, 50min or 60min).
In method of the present invention, in step (2), the rectifying can be real in such a way that this field is conventional It applies.Oil can be mutually cut into gasoline fraction, diesel oil distillate and heavy oil component (also referred to as residual oil) during the rectifying.Institute State gasoline fraction and the diesel oil distillate optionally deployed after be used as gasoline products or diesel product.The heavy oil component can To be applied to other feedstock oil processing technologys as raw material.
In method of the present invention, the solid phase isolated in separation of solid and liquid process described in step (2) is mainly iron Component can be used as catalytic agent reuse in the hydrogenation reaction described in step (1), it is also possible to make other industrial chemicals, such as can In manufacture craft for coating article.
The present invention will be described in detail by way of examples below, but scope of protection of the present invention is not limited thereto.
Embodiment 1
It takes 1000g steel scrap ROLLING OIL to be added in reaction kettle, hydrogen is then passed through into reaction kettle, reaches hydrogen partial pressure 3.5MPa, hydrogen to oil volume ratio 500 are warming up to 280 DEG C, insulation reaction 3h under stiring.
Operation is centrifuged to the mixture after reaction, centrifugal rotational speed 3500rpm, centrifugation time 10min divide Separate out solid phase.
It the liquid phase after solid phase will be isolated is put into rectifying column and carry out rectifying, collect gasoline fraction, diesel oil distillate and heavy oil Component, as a result as shown in table 1 below.
Embodiment 2
It takes 1000g steel scrap ROLLING OIL to be added in reaction kettle, hydrogen is then passed through into reaction kettle, reaches hydrogen partial pressure 4MPa, hydrogen to oil volume ratio 500 are warming up to 300 DEG C, insulation reaction 2h under stiring.
Operation is centrifuged to the mixture after reaction, centrifugal rotational speed 4000rpm, centrifugation time 8min divide Separate out solid phase.
It the liquid phase after solid phase will be isolated is put into rectifying column and carry out rectifying, collect gasoline fraction, diesel oil distillate and heavy oil Component, as a result as shown in table 1 below.
Embodiment 3
It takes 1000g steel scrap ROLLING OIL to be added in reaction kettle, hydrogen is then passed through into reaction kettle, reaches hydrogen partial pressure 4.5MPa, hydrogen to oil volume ratio 500 are warming up to 320 DEG C, insulation reaction 1.5h under stiring.
Operation is centrifuged to the mixture after reaction, centrifugal rotational speed 4000rpm, centrifugation time 10min divide Separate out solid phase.
It the liquid phase after solid phase will be isolated is put into rectifying column and carry out rectifying, collect gasoline fraction, diesel oil distillate and heavy oil Component, as a result as shown in table 1 below.
Embodiment 4
Steel scrap ROLLING OIL is recycled according to the method for embodiment 3, the difference is that additionally adding into reaction kettle Enter 10g Raney's nickel, the analysis result of product is as shown in table 1 below.
Embodiment 5
Steel scrap ROLLING OIL is recycled according to the method for embodiment 3, the difference is that additionally adding into reaction kettle Enter 50g toluene, the analysis result of product is as shown in table 1 below.
Comparative example 1
1000g steel scrap ROLLING OIL is taken, is directly placed into rectifying column and carries out rectifying.As a result, steel scrap ROLLING OIL can not be isolated Oily phase and solid phase.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Solid phase components 375g 371g 368g 376g 378g
Gasoline fraction 257g 253g 263g 247g 256g
Diesel oil distillate 211g 223g 207g 229g 221g
Heavy oil component 157g 153g 162g 148g 145g
It according to the method described in the present invention can be real it can be seen from above-described embodiment and comparative example and the data of table 1 Now steel scrap ROLLING OIL is recycled, specifically, gasoline and diesel oil distillate can be recycled from steel scrap ROLLING OIL, is realized useless The recycling treatment of steel rolling oil.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to Protection scope of the present invention.

Claims (8)

1. a kind of steel scrap ROLLING OIL recycling processing method, which comprises the following steps:
(1) in the presence of the catalysts and solvents of optional addition, steel scrap ROLLING OIL is made to carry out hydrogenation reaction in hydrogen atmosphere;
(2) mixture after reaction is separated by solid-liquid separation, the liquid phase isolated is subjected to rectifying, gasoline is obtained and diesel oil evaporates Point.
2. the method according to claim 1, wherein hydrogen divides in the hydrogenation process described in step (1) Pressure is 2-15MPa.
3. the method according to claim 1, wherein reaction is warm in the hydrogenation process described in step (1) Degree is 250-370 DEG C.
4. method described in any one of -3 according to claim 1, which is characterized in that the dosage of the catalyst is described useless The 0-10% of steel rolling oil weight.
5. method described in any one of -3 according to claim 1, which is characterized in that solvent described in step (1) be toluene, At least one of benzene, methanol and ethyl acetate.
6. according to the method described in claim 5, it is characterized in that, the dosage of the solvent is the steel scrap ROLLING OIL weight 0-200%.
7. method described in any one of -3 according to claim 1, which is characterized in that in step (2), the separation of solid and liquid To filter or being centrifugated.
8. method described in any one of -3 according to claim 1, which is characterized in that the method also includes: by solid-liquid point It is back in hydrogenation reaction described in step (1) from the solid phase isolated in the process.
CN201910083336.1A 2019-01-28 2019-01-28 A kind of steel scrap ROLLING OIL recycling processing method Pending CN109797002A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102465004A (en) * 2010-11-10 2012-05-23 财团法人工业技术研究院 Method for modifying oil product
CN102504865A (en) * 2011-11-15 2012-06-20 安徽盈荣生物能源科技有限公司 Method for refining diesel oil or gasoline by using waste oil
CN202961912U (en) * 2012-11-30 2013-06-05 重庆现代石油(集团)有限公司 Rolling oil regeneration system
CN105754706A (en) * 2016-04-26 2016-07-13 上海应用技术学院 Method for regenerating waste rolling oil

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102465004A (en) * 2010-11-10 2012-05-23 财团法人工业技术研究院 Method for modifying oil product
CN102504865A (en) * 2011-11-15 2012-06-20 安徽盈荣生物能源科技有限公司 Method for refining diesel oil or gasoline by using waste oil
CN202961912U (en) * 2012-11-30 2013-06-05 重庆现代石油(集团)有限公司 Rolling oil regeneration system
CN105754706A (en) * 2016-04-26 2016-07-13 上海应用技术学院 Method for regenerating waste rolling oil

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