CN1195830C - Paraffin adsorption refining method - Google Patents
Paraffin adsorption refining method Download PDFInfo
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- CN1195830C CN1195830C CNB021096732A CN02109673A CN1195830C CN 1195830 C CN1195830 C CN 1195830C CN B021096732 A CNB021096732 A CN B021096732A CN 02109673 A CN02109673 A CN 02109673A CN 1195830 C CN1195830 C CN 1195830C
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- paraffin
- refining
- spent catalyst
- hydrofining
- sorbent material
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a method for refining paraffin by using a hydrorefining waste catalyst as an absorbing agent. The present invention is characterized in that a treated hydrorefining waste catalyst is used as a paraffin refining absorbing agent; the refining temperature is from 90 DEG C to 200 DEG C and the airspeed is from 0.1 to 5.0 (l/h); the paraffin can be refined by an intermittent technological process and a continuous technological process; the absorbing agent can be regenerated. The method can be used for singly refining the paraffin and cooperating with a hydrorefining process as the preprocessing of hydrorefining raw wax to prolong the service life of a hydrogenation catalyst.
Description
1, technical field
The invention belongs to paraffin purification techniques field, specifically the present invention relates to a kind of paraffin adsorption refining method, and a kind of sorbent material of this method use.
2, background technology
Paraffin production is that the VGO cut with paraffinic crude is a raw material, obtain the wax material that oil-containing and fusing point meet index request through solvent dewaxing and de-oiling, because impurity (as sulfide, nitride, aromatic hydrocarbons and colloid etc.) is more in the wax material, all can exert an adverse impact to the color of paraffin, light stability etc.So wax material needs further to make with extra care to remove undesirable components, to adapt to various needs.
Be used for paraffin purified method at present, acid-alkali refining, refining with adsorbents and hydrofining are arranged.Acid-alkali refining not only produces a large amount of acid sludges, alkaline residue, contaminate environment, and have the equipment corrosion problem, so method does not re-use substantially.Hydrofining is with the undesirable components in the wax, and sulphur, nitrogen and oxygen are with H
2S, NH
3And H
2The form of O is removed, and makes aromatic hydrocarbons and alkene etc. become stable hydrocarbon, reaches the purified purpose.This technology has simple to operate, and is convenient, yield height, advantage such as pollution-free.But the matching requirements height, investment is big, and complex process operate also difficultly, and for the low enterprise of paraffin throughput, employing hydrofining is also uneconomical.
Refining with adsorbents then suitability is wider, and the sorbent material that uses aspect paraffin is the powder activity carclazyte now, though the powder carclazyte has bigger specific surface area and stronger adsorption activity, the powder carclazyte can not be regenerated, and the useless carclazyte of generation is contaminate environment also.
Patent CN1161367A discloses a kind of catalytic cracking spent catalyst and atlapulgite of adopting and has mixed the compound adsorbent that forms, and is used for the refining of paraffin.Technological process is periodical operation, and compound adsorbent can not be regenerated.
Patent CN1071446A adopts refining with adsorbents rice bran wax and natural wax thereof, and the sorbent material of selecting for use is AL
2O
3, compound adsorbent such as silicon bath soil, polymeric amide, methacrylic resin.Granularity 100-200 order, refining wax yield 74%-91% product is a white or light yellow.Make solvent with stable hydrocarbon (as sherwood oil), be mixed with solution with wax and make with extra care, and, with this solvent wash adsorption column, through distill product, solvent recuperation, sorbent material can be recycled through regeneration.This method uses solvent as thinner, so separating solvent has increased energy consumption.
Br9305266 makes sorbent material with aluminum oxide, and the fixed bed percolation filtration treating is removed the impurity in the Microcrystalline Wax.Aluminum oxide aperture 50～100 , acid 400 μ mol/cm
3, 110～130 ℃ of extraction temperatures.This method is used for the refining of Microcrystalline Wax.
At present, the most hydrofinishing process that adopt of some enterprises that the paraffin turnout is bigger, in addition in most oil refining enterprises, also has larger petroleum products hydro-refining unit, the employed catalyzer of these hydro-refining units all has certain life-span, and consequent spent catalyst is the difficult solid waste that reclaims, handles.
3, summary of the invention
The present invention is directed to the above-mentioned problems in the prior art, a kind of method of utilizing the hydrofining spent catalyst to be used for paraffin adsorption refining is provided.
Hydrobon catalyst is that the oxide compound with Si, Al or Si/Al is a carrier, and is loaded with the hydrogenation active metals component.Such catalyzer aperture is even, and specific surface area is big.The hydrofining spent catalyst is because the accumulation of pollutent, its physico-chemical property has had bigger variation, can not be used for other physics, chemical process generally speaking, but discover to have stronger absorption through the hydrofining spent catalyst after certain processing for paraffin and take off the impurity ability by experiment.Based on above-mentioned discovery, the present invention proposes following paraffin adsorption refining technology.
Method of the present invention be will be useless Hydrobon catalyst at the gaseous media that contains oxygen 0.1m%～20m%, under 300～600 ℃ of (preferred 400～600 ℃) conditions, handle 5～100 hours (preferred 12～72 hours).In the adsorber of packing into that will handle well then, under 90 ℃～200 ℃ extraction temperatures, wax material can obtain qualified wax product with 0.1～5.0 hour-1 air speed by sorbent material.The processing power of unit sorbent material is 50～100g/g catalyzer.Sorbent material behind the inactivation can be regenerated.
The present invention but select diesel oil, lubricating oil distillate for use, and the hydrofining spent catalyst of paraffin are used for the refining with adsorbents of paraffin after treatment.Paraffin adsorption refining can adopt the continous way working method, also can adopt the batch operation method.
The condition of the adsorbent reactivation behind the inactivation is: regenerate under the gas condition that contains oxygen 1%～20%, constant temperature is 10～40 hours under 400 ℃～600 ℃ temperature.
The inventive method can be used for paraffin adsorption refining separately, produces the technology of qualified product, also can be used for combining with hydrorefining paraffin wax, as the pre-treatment of hydrofining wax material, improves Hydrobon catalyst work-ing life, and has reduced the refining cost of paraffin.
Compare with existing sorbent material, sorbent material of the present invention is a spent catalyst, and its advantage is: the price of sorbent material is dirt cheap, and can reduce the paraffin production cost; Can be suitable for continuous operation, also can be used for periodical operation; Process for purification is fairly simple, easy handling; The loss for the treatment of process wax product is few, the yield height; Sorbent material can carry out reprocessing cycle to be used; Reduce the pollution of spent catalyst to environment.
4, embodiment
Below in conjunction with embodiment, specify the solution of the present invention and effect.
Testing used sorbent material, is the 481-2B hydrofining spent catalyst produced of the FV that produces of after treatment Qilu Petrochemical company and Shenyang Catalyst Plant under certain condition.Raw material is No. 58 fully refined wax material, and its feedstock property is analyzed: oil-containing 0.2m%, Sai Shi colorimetric+No. 12, light stability 6～7, penetration degree 14 (1/10mm).
Embodiment 1
With the gaseous media of oxygen level 1% by FV spent catalyst layer, elevated temperature progressively, constant temperature is 48 hours when catalyst temperature reaches 450 ℃.With the catalyzer after handling, the diameter 10mm that packs into, in the reactor of long 500mm, the high 100mm of bed, 120 ℃ of adsorption temps, paraffin is with 0.5h
-1Air speed is led to 150 hours material time by sorbent material.Product wax oil-containing 0.21m%, Sai Shi colorimetric＞No. 30, No. 3, light stability, penetration degree 14, wax fusing point 58.5, product yield 99.8m%.
Embodiment 2
With the gaseous media of oxygen level 5% by FV spent catalyst layer, elevated temperature progressively, constant temperature is 30 hours when catalyst temperature reaches 500 ℃.At the reaction conditions identical, 170 ℃ of adsorption temps, paraffin air speed 2.0h with embodiment 1
-1, logical 40 hours material time, product wax oil-containing 0.20m%, Sai Shi colorimetric＞No. 30, light stability＜No. 4, penetration degree 14, wax fusing point 58.3, product yield 99.7m%.
Embodiment 3
With the gaseous media of oxygen level 10% by FV spent catalyst layer, elevated temperature progressively, constant temperature is 24 hours when catalyst temperature reaches 550 ℃.Under the identical condition of reaction conditions and adsorption temp condition and embodiment 1, the raising air speed is 4.0h
-1, logical 20 hours material time, product wax oil-containing 0.20m%, Sai Shi colorimetric＞No. 28, No. 4, light stability, penetration degree 14, wax fusing point 58.6, product yield 99.8m%.
Embodiment 4
The sorbent material of inactivation through after suitably handling, is regenerated containing under the gaseous media condition of oxygen 5%, and elevated temperature progressively was 480 ℃ of left and right sides constant temperature 30 hours.The reactor of then reproducing adsorbent being packed under the identical situation of adsorption conditions and embodiment 1, carries out adsorption test, wax product rerum natura oil-containing 0.22m%, Sai Shi colorimetric＞No. 30, light stability＜No. 4, penetration degree 14, wax fusing point 58.4, product yield 99.6m%.It is fine that adsorbent activity is recovered.
Embodiment 5
With the gaseous media of oxygen level 5% by 481-2B spent catalyst layer, elevated temperature progressively, constant temperature is 36 hours when catalyst temperature reaches 550 ℃.With the catalyzer after handling, the diameter 10mm that packs into, in the reactor of long 500mm, the high 100mm of bed, 120 ℃ of adsorption temps, paraffin is with 0.5h
-1Air speed is led to 140 hours material time by sorbent material.Product wax oil-containing 0.23m%, Sai Shi colorimetric＞No. 30, No. 3, light stability, penetration degree 14, wax fusing point 58.5, product yield 99.6m%.
Embodiment 6
With the gaseous media of oxygen level 1% by 481-2B spent catalyst layer, elevated temperature progressively, constant temperature is 30 hours when catalyst temperature reaches 600 ℃.At the reaction conditions identical, 160 ℃ of adsorption temps, paraffin air speed 2.0h with embodiment 1
-1, logical 55 hours material time, product wax oil-containing 0.19m%, Sai Shi colorimetric＞No. 30, light stability＜No. 4, penetration degree 14, wax fusing point 58.1, product yield 99.7m%.
Embodiment 7
With the gaseous media of oxygen level 1% by 481-2B spent catalyst layer, elevated temperature progressively, constant temperature is 72 hours when catalyst temperature reaches 450 ℃.Under the identical condition of reaction conditions and adsorption temp condition and embodiment 1, the raising air speed is 4.0h
-1, logical 20 hours material time, product wax oil-containing 0.20m%, Sai Shi colorimetric＞No. 28, light stability＜No. 4, penetration degree 14, wax fusing point 58.6, product yield 99.1m%.
Embodiment 8
The sorbent material of inactivation is carried out manipulation of regeneration, regenerate containing under the gaseous media condition of oxygen 10%, elevated temperature progressively was 540 ℃ of left and right sides constant temperature 15 hours.The reactor of then reproducing adsorbent being packed under the identical situation of adsorption conditions and embodiment 5, carries out adsorption test, wax product rerum natura oil-containing 0.20m%, Sai Shi colorimetric＞No. 29, light stability＜No. 4, penetration degree 14, wax fusing point 58.3, product yield 99.4m%.It is fine that adsorbent activity is recovered.
Show from the test-results of embodiment, the sorbent material that the present invention selects for use, refining effect is more satisfactory, and makes the hydrofining spent catalyst be able to better utilised, also has remarkable economic efficiency simultaneously.
Claims (5)
1, a kind of paraffin adsorption refining method contacts paraffin with sorbent material, it is characterized in that employed sorbent material is treated hydrofining spent catalyst; Described refining with adsorbents condition is: 90 ℃～200 ℃ of temperature, and wax material volume space velocity 0.1～5.0 hour-1, the processing power of unit sorbent material is 50～100g/g catalyzer; The treatment process of described hydrofining spent catalyst was handled 5～100 hours under 300～600 ℃ of conditions for using the gaseous media that contains oxygen 0.1m%～20m%.
2, according to the described paraffin adsorption refining method of claim 1, the treatment temp that it is characterized in that described hydrofining spent catalyst is 400～600 ℃, and the treatment time is 12～72 hours.
3,, it is characterized in that regenerating behind the described sorbent material inactivation according to the described paraffin adsorption refining method of claim 1.
4,, it is characterized in that described hydrofining spent catalyst is selected from the hydrofining spent catalyst of diesel oil, lubricating oil, paraffin according to the described paraffin adsorption refining method of claim 1.
5,, it is characterized in that described refining with adsorbents process is for operating or batch operation with continous way according to the described paraffin adsorption refining method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021096732A CN1195830C (en) | 2002-05-15 | 2002-05-15 | Paraffin adsorption refining method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021096732A CN1195830C (en) | 2002-05-15 | 2002-05-15 | Paraffin adsorption refining method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1458245A CN1458245A (en) | 2003-11-26 |
| CN1195830C true CN1195830C (en) | 2005-04-06 |
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ID=29426238
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021096732A Expired - Lifetime CN1195830C (en) | 2002-05-15 | 2002-05-15 | Paraffin adsorption refining method |
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| CN (1) | CN1195830C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102385590B1 (en) | 2014-07-17 | 2022-04-11 | 사빅 글로벌 테크놀러지스 비.브이. | Upgrading hydrogen deficient streams using hydrogen donor streams in a hydropyrolysis process |
| CN106047411A (en) * | 2016-05-12 | 2016-10-26 | 辽宁凯迈石化有限公司 | Paraffin refinement and regeneration method and system |
| CN107434983B (en) * | 2017-08-10 | 2019-04-12 | 合肥市田源精铸有限公司 | A kind of recycling processing method of founding wax material |
| CN109988627B (en) * | 2017-12-29 | 2021-07-09 | 中国石油化工股份有限公司 | Flexible paraffin hydrogenation process |
| CN110240935A (en) * | 2019-06-13 | 2019-09-17 | 国家能源投资集团有限责任公司 | Hydrogenation system and method for hydrotreating |
| CN116410794A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气股份有限公司 | Refining method of high-melting-point crude paraffin |
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2002
- 2002-05-15 CN CNB021096732A patent/CN1195830C/en not_active Expired - Lifetime
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| CN1458245A (en) | 2003-11-26 |
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