CN1062894C - Method for producing vaseline - Google Patents
Method for producing vaseline Download PDFInfo
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- CN1062894C CN1062894C CN97122141A CN97122141A CN1062894C CN 1062894 C CN1062894 C CN 1062894C CN 97122141 A CN97122141 A CN 97122141A CN 97122141 A CN97122141 A CN 97122141A CN 1062894 C CN1062894 C CN 1062894C
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- vaseline
- catalyst
- conversion zone
- refining
- protective material
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Abstract
The present invention discloses a hydrofining method for vaseline. A protective agent and a refining catalyst which use the metals of the VIB group and the VIII group as active components are adopted by the method, two sections of hydrogenation processes are adopted, and then, the raw materials of the vaseline are deeply refined under the operating pressure of 5.0 to 25.0MPa. Thus, the service life of the catalyst can be prolonged, the production cost can be reduced, and the operation process can be simplified; vaseline products with high quality are obtained for medicines and cosmetics.
Description
The present invention relates to a kind of process for purification of producing Vaseline, particularly adopt the high-quality Vaseline product of hydrogenation method direct production.
Vaseline is the raw materials for production of important medicine, daily-use chemical industry and other fine chemical product.The production process of Vaseline mainly is made of the blending of raw material and refining two portions of raw material, owing to containing undesirable components such as more condensed-nuclei aromatics and sulphur, nitrogen, oxygen helerocyclics in the Vaseline raw material, must carry out deep refining it is removed.The Vaseline that is applied in medicine and the makeup must be accomplished harmless.Therefore refining is the committed step of producing Vaseline.
Traditional Vaseline process for purification is a sour carclazyte method and an alchlor process.Shortcomings such as these two kinds of methods have all that yield is low, the three wastes are high, poor product quality and complicated operation.
It is a kind of new Vaseline production method that hydrogenation method is produced Vaseline.This method can be with the sulphur in the Vaseline raw material, nitrogen, oxygen helerocyclics effective elimination, and the aromatic hydrocarbons in the Vaseline raw material is converted into stable hydrocarbon.This method is three-waste free pollution in process of production, can produce high yield, high-quality Vaseline product.
USSR (Union of Soviet Socialist Republics) patent SU 925988 introduces a kind of Vaseline process for purification, this method adopts the one-stage hydrogenation flow process, hydrogenation reaction is carried out under temperature 325-370 ℃, pressure 4.0-5.0MPa, hydrogenated products must could be produced high-quality Vaseline product through carclazyte refining with adsorbents, and its technology is comparatively loaded down with trivial details.
U.S. Pat 2998377 is introduced a kind of Vaseline process for purification, and this method adopts one-stage hydrogenation flow process, 370 ℃ of hydrogenation reaction temperature, pressure 21MPa, volume space velocity 0.5h
-1, hydrogen to oil volume ratio 354.This patented technology has adopted higher working pressure, although can obtain to meet the Vaseline product of certain mass standard, is unfavorable for reducing plant investment and safety operation.
In above-mentioned Vaseline hydrogen addition technology, the investment of high-pressure hydrogenation method industrial installation is high, processing safety is poor.When reaction pressure is low,, need clay finishing auxilliary mutually again because refining depth is not enough, thus cause technical process length, complicated operation, yield is low and shortcoming such as three-waste pollution is arranged.In addition, because the Vaseline raw materials for production mainly come from the residual oil slack wax, wherein must contain a certain amount of metal, as impurity such as iron, zinc, lead, calcium.The existence of these impurity, though can remove its overwhelming majority in treating process, because common Hydrobon catalyst demetalization poor performance, it is low to hold the metal ability, running period is long slightly, just have part metals impurity and residue among the product, its quality is descended, and more serious problem is, a large amount of metallic impurity are in the aperture of Hydrobon catalyst deposition, make rapid catalyst deactivation, have a strong impact on catalyzer work-ing life and running period, production cost increases.
Discover that in the hydrofining of petroleum fractions, organometallics and sulfide contained in the raw material react, the solid metal sulfide precipitation of generation is in the hole of catalyzer.The always parallel generation of demetalization reaction of petroleum fractions with refining reaction, and the demetalization process also is the process of the contaminated and active reduction of catalyzer.For catalyst for refining, its aperture is many in the micropore district of＜10nm, because the aperture is less, metallic sulfide causes between the catalyzer aperture and the obstruction between the particle easily at the aperture and the surface deposition of catalyzer, makes catalyst activity reduction.Simultaneously, to pollute also be one of reason of weakening of catalyst strength to metallic sulfide.In the hydrofining of heavy distillate, raw material institute containing metal is a major reason of catalyst deactivation in the aperture of catalyzer deposition.Therefore, when metal content in the hydrofining raw material during, should take special measure that it is removed, to guarantee the work-ing life and the running period of catalyzer greater than 10 μ g/g.The component that 30-80w% is arranged in the Vaseline raw material is from vacuum residue fraction, and its metal content is generally 20-100 μ g/g, therefore, should at first metal be removed, to prolong the work-ing life of catalyst for refining.The aperture of existing catalyst for hydrogenation refining of Vaseline is between 3-10nm, and so the catalyzer in aperture is not easy to make the organo-metallic molecular diffusion to the inner uniform deposition of granules of catalyst.And simply select macroporous catalyst for use, though can improve metal removal rate, senior general is crossed in the aperture influences the desulfurization removing nitric effect.
The objective of the invention is to overcome the shortcoming of existing Vaseline production technology, propose a kind of hydrogenation refining of Vaseline method.This method is selected protective material (catalyst for demetalation) and two types of catalyzer of catalyst for refining for use, prolongs the work-ing life and the running period of catalyzer, reduces production costs.This method can adopt the working pressure of 5.0-25.0MPa, when adopting lower working pressure, can avoid the shortcomings such as plant investment height that cause because of hypertonia, still can obtain high-quality Vaseline product simultaneously; When adopting higher working pressure, can improve air speed, thereby improve the processing power of device.This method does not adopt clay finishing, thereby simplifies the operation, improves product yield, further improves the quality of products.
To the effect that of the present invention, select for use not only to have good hydrofining and aromatic hydrocarbons saturation properties, but also have good optionally catalyst for refining and select protective material (catalyst for demetalation) for use with demetalization function.Protective material mean pore size 20～30nm, the macropore capacity of＞50nm account for ratio＞10% of total pore capacities.Adopt two-section hydrotreating technology, first conversion zone pack into protective material and catalyst for refining, reaction bed top is protective material, the bottom is a catalyst for refining.Second conversion zone catalyst for refining of packing into.The catalyst for refining that two conversion zones are packed into can be with a kind of catalyzer, also can be different catalyzer.The volume ratio of protective material Intake Quantity and the total Intake Quantity of catalyst for refining is 1: 10-40.The volume ratio of first conversion zone and the second conversion zone catalyst for refining Intake Quantity is 1: 0.5-2.5.The active metal component of protective material and catalyst for refining is VI B family and VIII family metal, and carrier is aluminum oxide or aluminum oxide silicon monoxide.What VI B family metal was recommended is molybdenum and tungsten, the protective material of first conversion zone and catalyst for refining special recommendation be molybdenum, the second conversion zone catalyst for refining special recommendation be tungsten.What VIII family metal was recommended is nickel and cobalt, special recommendation be nickel.The metal content MoO of the molybdenum of special recommendation, nickel protective agent
3Be 2.0～12.0w%, NiO is 0.5～6.0w%.
Specifically, the Vaseline raw material mixes with hydrogen, and the heating back enters first conversion zone by top, mainly carries out the reaction of demetalization and desulfurization removing nitric.First section reaction product enters second conversion zone by top after lowering the temperature, mainly carry out the aromatic hydrocarbons saturated reaction.The operational condition of first and second conversion zone is: first section hydrogen dividing potential drop 5.0-25.0MPa, volume space velocity 0.1-0.8h
-1(with respect to protectant volume space velocity is 0.5-8.0h
-1), temperature 300-400 ℃, hydrogen to oil volume ratio 300-1000; Second section hydrogen dividing potential drop 5.0-25.0MPa, volume space velocity 0.1-0.8h
-1, temperature 200-300 ℃, hydrogen to oil volume ratio 300-1000.The refined products of coming out from second conversion zone bottom promptly obtains can be used for the Vaseline product of medicine and makeup after stripping, drying.
Compare according to the method for the invention production Vaseline and high-pressure hydrogenation method, working pressure can extend to middle pressure, has improved the handiness of device, when pressing in the employing, helps safety operation, reduces plant investment; Compare with the medium-pressure hydrocracking method, do not need clay finishing, simple to operate, the product yield height, production cost is low, three-waste free discharge.With do not add protectant process for purification relatively, can prolong the work-ing life and the running period of catalyzer.
Produce Vaseline according to the inventive method, quality product meets medical white vaseline national standard (GB1790), make up level Vaseline industry standard (SH0008) and medical white vaseline version British Pharmacopoeia (BP-93) in 1993 standard.
Further specify the present invention below by embodiment.
The embodiment of the invention and comparative example all adopt with a kind of Vaseline raw material, and its character sees Table 1.
The embodiment of the invention and comparative example all carry out on the small-sized trickle bed hydrogenation unit of continous way.The first conversion zone protective material is 1: 10 with catalyst for refining admission space ratio, and first conversion zone is 1: 1 with the second conversion zone catalyst for refining admission space ratio.The chemical constitution of selected catalyzer sees Table 2.
The operational condition of the embodiment of the invention and comparative example sees Table 3, and the protective material metal removal effect sees Table 4,2000 hours longevity tests and the results are shown in Table 5, and the embodiment quality product sees Table 6.
Table 1 Vaseline feedstock property
| Project | The result | Project | The result |
| Dropping point, ℃ | 47.0 | N,μg·g -1 | 317 |
| Cone penetration (25 ℃), 1/10mm | 165 | Fe,μg·g -1 | 6.13 |
| Acid number, mgKOHg -1 | 1.87 | Zn,μg·g -1 | 36.75 |
| Ultraviolet extinction value (290nm) | 0.596 | Pb,μg·g -1 | 0.85 |
| S,μg·g -1 | 732 | Ca,μg·g -1 | 1.76 |
| Condensed-nuclei aromatics (265-420nm extinction value maximum value) | 4.508 |
Table 2 catalyst chemical is formed
| Project | Cat1 (molybdenum nickel type protective material) | Cat2 (molybdenum nickel type catalyst for refining) | Cat3 (tungsten nickel type catalyst for refining) |
| MoO 3,w％ | 9.6 | 19.4 | |
| WO 3,w％ | 29.5 | ||
| NiO,w％ | 4.2 | 5.2 | 6.6 |
| Al 2O 3,w％ | Surplus | Surplus | Surplus |
Table 3 Vaseline hydroprocessing condition
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| The hydrogen dividing potential drop, MPa | 6.5 | 6.5 | 14.0 | 6.5 | 6.5 |
| Hydrogen to oil volume ratio | 500 | 500 | 500 | 500 | 500 |
| First conversion zone | |||||
| Catalyzer | Cat1 | Cat1+Cat2 | Cat1+Cat2 | Cat2 | Cat2 |
| Temperature, ℃ | 330 | 330 | 330 | 330 | 330 |
| Air speed, h -1 | 3.2 | 0.3 | 0.6 | 0.3 | 0.3 |
| Second conversion zone | |||||
| Catalyzer | Cat3 | Cat3 | Cat2 | Cat2 | |
| Temperature, ℃ | 250 | 250 | 250 | 330 | |
| Air speed, h -1 | 0.3 | 0.6 | 0.3 | 0.3 |
Table 4 protective material metal removal effect
| Project | Fe,μg·g -1 | Zn,μg·g -1 | Ca,μg·g -1 | Pb,μg·g -1 |
| Raw material | 6.13 | 36.75 | 1.76 | 0.86 |
| Product | 0.33 | 3.34 | 0.19 | 0.06 |
| Decreasing ratio, w% | 94.6 | 90.9 | 89.2 | 92.9 |
Table 4 shows, more than 89w%, metal removal effect is fairly obvious to protective material to the demetallization per of Vaseline raw material.Vaseline raw material after the demetalization enters the catalyst for refining bed, got rid of the deposition of metallic sulfide in the catalyzer aperture, can keep the unimpeded of catalyst for refining duct for a long time, thereby guarantee carrying out smoothly of desulfurization removing nitric and aromatic hydrocarbons saturated reaction, prolong the work-ing life of catalyst for refining.
2000 hours longevity test results of table 5 catalyzer
| Project | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Target value |
| S in the product, μ gg -1 | 6.9 | 5.2 | 16.7 | 13.0 | <20 |
| N in the product, μ gg -1 | 11.1 | 10.9 | 23.7 | 17.5 | <30 |
| Condensed-nuclei aromatics (265-420nm extinction value maximum value) | 0.32 | 0.28 | 1.25 | 1.65 | <1.05 |
As can be seen from the above table, through 2000 hours continuous operation, though the sulphur nitrogen index of comparative example 1,2 still meets the requirements, the desulfurization removing nitric ability of catalyzer obviously reduced.Condensed-nuclei aromatics is to guarantee one of judgement index that medicinal vaseline is harmless, and the condensed-nuclei aromatics of comparative example 1,2 all exceeds standard, and quality product does not meet medical white vaseline standard.And the sulphur nitrogen of embodiment 2,3 and condensed-nuclei aromatics index are significantly less than comparative example 1,2, the requirement of quality product conformance with standard, show 2000 hours after, catalyst for refining is still keeping higher activity, has embodied and has used protectant advance.
Table 6 Vaseline quality product
| Project | Embodiment 2 | Implement sharp 3 | GB1790 | BP-93 |
| Color | Be shallower than color solution A | Be shallower than color solution A | Be shallower than color solution A | |
| Dropping point, ℃ | 47.5 | 47.0 | 45-55 | 42-60 |
| Cone penetration (25 ℃), 1,10mm | 165 | 171 | 130-250 | |
| Organic acid, mgNaOH.g -1 | 0.00 | 0.00 | ≤0.08 | ≤0.10 |
| Water-soluble soda acid | Do not have | Do not have | Do not have | |
| Opposite sex organism | Do not have | Do not have | Do not have | |
| Sulfated ash, % | 0.00 | 0.00 | ≤0.05 | ≤0.10 |
| The sulfide test | Qualified | Qualified | Qualified | Qualified |
| Ultraviolet extinction value (290nm) | 0.072 | 0.026 | ≤0.50 | ≤0.50 |
| Condensed-nuclei aromatics (265-420nm extinction value maximum value) | 0.25 | 0.19 | ≤ 278nm is liquid extinction value (1.05) how |
Quality product meets medical white vaseline national standard (GB1790) and medical white vaseline British Pharmacopoeia (BP-93) standard in the table 6.
Claims (5)
1. the method for Vaseline is produced in a hydrofining; the Vaseline raw materials for production are contacted with Hydrobon catalyst; remove condensed-nuclei aromatics and sulphur; nitrogen; oxygen helerocyclics; it is characterized in that the Vaseline raw materials for production with before Hydrobon catalyst contacts at first through a segment protect agent bed; the operational condition of this bed is identical with Hydrobon catalyst; its admission space is 1 with the ratio of Hydrobon catalyst admission space: 10-40; protective material is a catalyst for demetalation; the average pore diameter 20-30nm of its carrier, the macropore capacity of bore dia＞50nm accounts for more than 10% of total pore capacities.
2. according to the method for claim 1, it is characterized in that said Hydrobon catalyst is divided into the operation of two conversion zones, the first conversion zone operational condition is hydrogen dividing potential drop 5.0-25.0MPa, volume space velocity 0.1-0.8h-1, temperature of reaction 300-400 ℃, hydrogen to oil volume ratio 300-1000; The second conversion zone operational condition is hydrogen dividing potential drop 5.0-25.0MPa, volume space velocity 0.1-0.8h-1, temperature of reaction 200-300 ℃, hydrogen to oil volume ratio 300-1000.
3. according to the method for claim 2, it is characterized in that pack into the ratio of volume of first conversion zone and the second conversion zone catalyst for refining is 1: 0.5-2.5.
4. according to the method for claim 2, it is characterized in that said protective material is contained in the upper end of first conversion zone.
5. according to the method for claim 1, it is characterized in that said protective material is with MoO
3With NiO be active metal component, Al
2O
3Or Al
2O
3-SiO
2Carrier, metal content MoO
3Be 2.0-12.0w%, NiO is 0.5-6.0w%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97122141A CN1062894C (en) | 1997-11-24 | 1997-11-24 | Method for producing vaseline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97122141A CN1062894C (en) | 1997-11-24 | 1997-11-24 | Method for producing vaseline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1218093A CN1218093A (en) | 1999-06-02 |
| CN1062894C true CN1062894C (en) | 2001-03-07 |
Family
ID=5176702
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97122141A Expired - Lifetime CN1062894C (en) | 1997-11-24 | 1997-11-24 | Method for producing vaseline |
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| Country | Link |
|---|---|
| CN (1) | CN1062894C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318547C (en) * | 2005-10-24 | 2007-05-30 | 长春惠工催化剂有限责任公司 | High activity catalyst for hydrogenation refining of Vaseline and preparation method and uses thereof |
| CN102453549A (en) * | 2010-10-14 | 2012-05-16 | 中国石油化工股份有限公司 | Production method of vaseline |
| CN103102989B (en) * | 2011-11-10 | 2015-11-18 | 中国石油化工股份有限公司 | A kind of method that Vaseline is deeply hydrodearomatized |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050736A (en) * | 1988-10-04 | 1991-04-17 | 切夫尔昂研究公司 | Use has the macrovoid catalyzer of prescribed value |
| CN1157315A (en) * | 1996-02-13 | 1997-08-20 | 荆门石油化工研究院 | One section series hydrogenation refining process |
-
1997
- 1997-11-24 CN CN97122141A patent/CN1062894C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050736A (en) * | 1988-10-04 | 1991-04-17 | 切夫尔昂研究公司 | Use has the macrovoid catalyzer of prescribed value |
| CN1157315A (en) * | 1996-02-13 | 1997-08-20 | 荆门石油化工研究院 | One section series hydrogenation refining process |
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| Publication number | Publication date |
|---|---|
| CN1218093A (en) | 1999-06-02 |
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Owner name: CHINA PETROCHEMICAL CORPORATION; CHINA PETROLEUM & Free format text: FORMER NAME OR ADDRESS: CHINA PETRO-CHEMICAL CORP.; FUSHUN PETROCHEMICAL INSTITUTE., CHINA PETROCHEMICAL CORP. |
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| CP01 | Change in the name or title of a patent holder |
Patentee after: China Petrochemical Group Corp. Patentee after: Sinopec Group Fushun Research Institute of Petroleum and Petrochemicals Patentee before: China Petrochemical Corporation Patentee before: Fushun Research Inst. of Petroleum Processing, China Petro-chem. Corp. |
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Granted publication date: 20010307 |