CN1358825A - Reforming raw material oleum spirit desulfurating agent and preparation method - Google Patents
Reforming raw material oleum spirit desulfurating agent and preparation method Download PDFInfo
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- CN1358825A CN1358825A CN 02112508 CN02112508A CN1358825A CN 1358825 A CN1358825 A CN 1358825A CN 02112508 CN02112508 CN 02112508 CN 02112508 A CN02112508 A CN 02112508A CN 1358825 A CN1358825 A CN 1358825A
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Abstract
The reformed raw oil precision desulfurizing agent uses nickel as active component, aluminium oxide as carrier and adds effective catalyst promoter. Said desulfurizing agent is specially applicable to remove micro sulfur residual in reformed raw oil after prehydrogenation and stripping dehydration operation, and can make sulfur content of raw oil reduce d to below 0.5 micro g.g(-1). It possesses high desulfurizing activity, long service life, low cost and has no toxic action on reformation catalyst, so that it can effectively protect its downstream reformation catalyst and make it produce normal working efficiency.
Description
Technical field: the invention belongs to the petrochemical catalyst technical field, be specifically related to a kind of reforming raw material oleum spirit desulfurating agent and preparation method thereof.
Background technology: catalytic reforming process is to produce aromatic hydrocarbons, improves a kind of effective ways of petroleum naphtha octane value.In order to improve process efficiency, having developed multiple in recent years is main active constituent with platinum, is two (many) metal reforming catalysts of auxiliary agent with rhenium or other component.Because two (many) metal reforming catalysts are very sensitive to sulfide, as long as there is trace sulfide to exist in the stock oil, will cause catalyzer " poisoning " and reduce activity and selectivity, cause the processed oil liquid yield to reduce and catalyzer shortening in work-ing life, cause shut-down when serious.Therefore will guarantee that catalytic reforming unit normally moves, the sulphur content that at first will satisfy stock oil is less than 0.5 μ gg
-1Below, avoid two (many) metal reforming catalysts to descend until shut-down significantly because of stock oil sulphur content high activity.
In this technical field, the reforming catalyst that uses has by contained active constituent classification at present: to contain the sweetening agent of zinc, based on nickeliferous sweetening agent, based on three classes such as sweetening agent of cupric.According to of the report of prior art＜sulphur to " 3741 " bimetallic catalyst influence on system operation〉(catalytic reforming communication 1984. № 3 P63-80) described, when service temperature is 180 ℃, uses " 0703 " sweetening agent that contains active ingredient zinc can obtain certain effect.But sweetening effectiveness is low.Cannot say for sure to demonstrate,prove the stable 0.5 μ gg that is controlled at of sulfur content in oil products
-1Below.Again according to prior art＜appended heterogeneous catalyst of the second stage of the project imported unit and sorbent material overview〉(1,980 6 15 P3 of Shanghai Petrochem. General Plant) described, the ADS-11 sweetening agent that contains active ingredient that UOP produces can be with the feed oil sulphur content by 1 μ gg
-1Be removed to 0.5 μ gg
-1Below, 1 year work-ing life, price height.Again according to prior art＜US P4113606〉described, the sweetening agent that contains active ingredient copper can be used for this process, but does not report the copper wastage of its desulfurization level and sweetening agent.
Summary of the invention: the objective of the invention is: propose a kind of reforming raw oil and after adding hydrogen formulation dehydration operation in advance, in the fixed-bed desulfurization, can remove the desulfurizing agent of residual minim sulfide in the upstream process.It can make the stock oil sulphur content drop to 0.5 μ gg
-1Below, it is desulphurizing activated good, does not produce the material of " murder by poisoning " reforming catalyst simultaneously.
Reforming raw material oleum spirit desulfurating agent of the present invention is to be carrier with the aluminum oxide, and nickel is active ingredient, and zinc oxide is promotor, by a certain percentage after the co-precipitation, through compression molding, obtained after prereduction again.
The composition proportioning of reforming raw material oleum spirit desulfurating agent of the present invention (precentagewise meter) nickel content (in nickel oxide) is 10～70%, is preferably in 15～50%; Zinc oxide content (in zinc oxide) is 10～60%, is preferably in 10～45%; Alumina content is 5～40%, is preferably in 5～30%.Nickel element in this sweetening agent adds with nickel oxide, nickelous carbonate, single nickel salt form, and preferably the form with nickel oxide or nickelous carbonate adds.Zinc element adds with zinc oxide, zinc carbonate, zinc nitrate form, preferably adds with zinc oxide, zinc carbonate form.Alumina catalyst support can add when precipitation nickelous carbonate or precipitation zinc carbonate, adds when being preferably in co-blended.
Reforming raw material oleum spirit desulfurating agent manufacture method of the present invention is:
1. with above-mentioned nickel oxide (nickelous carbonate, nickelous nitrate), zinc oxide (zinc carbonate, zinc oxide), materials such as aluminum oxide are by the certain percentage ball grinder ball milling of packing into.
2. taking out raw materials mixed adding distilled water rolls.
3. the raw material that will roll carries out granulation.
4. particle carries out roasting.
5. after mixing, carry out compressing tablet on tabletting machine, general requirements is 3.5 * 2～4 millimeters tablets of Φ.
6. tablet activates under hydrogen-containing gas, and temperature control is as follows:
200±5℃——→340±5℃——→500±5℃
Activation in 2 hours 2 hours 2 hours is finished after naturally cooling is desulfurizing agent for reforming stock oil product of the present invention.
The product physicals:
Specific surface: 40～90m
2/ g
Pore volume: 0.20～0.34ml/g
Intensity: 〉=120N/cm
Particle diameter: Φ 3.5 * 2～4mm
The product analysis result:
| Composition | ??NiO | ??ZnO | ??Al 2O 3 | Other |
| ??wt％ | ??20～40 | ??16～38 | ??8～19 | ??2.6～8 |
Reforming raw material oleum spirit desulfurating agent of the present invention will reduce in use, and condition is: 200 ± 5 ℃ of temperature, the time is more than 12 hours, normal pressure, medium H
2+ N
2Or H
2+ H
2O steam, air speed are 100～300h
-1, density of hydrogen 5-100%.
Reforming raw material oleum spirit desulfurating agent working conditions of the present invention is:
Service temperature: room temperature～360 ℃
Working pressure: 0～15MPa
Liquid air speed: 1～12h
-1
Reforming raw material oleum spirit desulfurating agent of the present invention in the fixed-bed desulfurization, has stock oil sulphur content 5 μ gg after reforming raw oil adds hydrogen deduction dehydration operation in advance
-1About be removed to 0.5 μ gg
-1Following result of use.Than present any sweetening agent efficient height, active good, the while does not produce the material of " poison " catalyzer.The manufacturing process of this sweetening agent is comparatively easy, long service life, and raw material is easy to get, and cost is lower.
Embodiment: the present invention is described in detail below in conjunction with embodiment.
The embodiment of the invention (precentagewise meter)
Example one: nickel oxide: zinc oxide: aluminum oxide=30: 30: 40
Example two: nickel oxide: zinc oxide: aluminum oxide=35: 40: 25
Example three: nickel oxide: zinc oxide: aluminum oxide=40: 50: 10
Most preferred embodiment: nickel oxide: zinc oxide: aluminum oxide=38: 45: 17
More than each Example formulations all by above-mentioned manufacture method manufacturing, product is desulfurizing agent for reforming stock oil of the present invention, its use properties is referring to table 1,2,3,4.
The subordinate list explanation:
Table 1. shows the nickeliferous ADS-11 sweetening agent of reforming raw material oleum spirit desulfurating agent efficiency ratio height.
Table 2. shows the zinciferous 0703 sweetening agent height of desulfurizing agent for reforming stock oil efficiency ratio.
Sweetening agent illustrated that still more than 95% the sweetening agent life-span is long when table 3. showed desulfurizing agent for reforming stock oil sulfur capacity 9%.
Table 1. reforming raw material oleum spirit desulfurating agent and ADS-11 contrast
Annotate: " stock oil " hurdle: 1 for adding the preceding oil product of hydrogen deduction dehydration in advance; 2 for mainly containing the oil product of organosulfur;
| Sequence number | The sweetening agent title | Stock oil | Operational condition | Stock oil sulphur content μ g g -1 | Self-cleaning oil sulphur content μ g g -1 | Sweetening agent Sulfur capacity % | Working time | ||
| Temperature ℃ | Pressure | Liquid air speed h -1 | |||||||
| ?1 | Reforming raw material oleum spirit desulfurating agent | ??2 ??1 | 180 | Normal pressure | 24 | 3.38 2.22 | 1.50 0.14 | 1.6 5 | ?11～50 ?51～ ?100 |
| ?2 | ADS-11 | ??2 ??1 | 180 | Normal pressure | 24 | 3.38 2.22 | 1.88 0.24 | 1.5 0 | ?11～50 ?51～ ?100 |
Table 2 reforming raw material oleum spirit desulfurating agent and 0703 contrast
| Sequence number | The sweetening agent title | Operational condition | Stock oil sulphur content μ gg -1 | Self-cleaning oil sulphur content μ gg -1 | ||
| Temperature ℃ | Pressure | Liquid air speed h -1 | ||||
| ??1 | Reforming raw material oleum spirit desulfurating agent | ??180 | Normal pressure | ??16 | ????1.21 | ??0.18 |
| ??2 | ????0703 | ??180 | Normal pressure | ??16 | ????1.21 | ??0.32 |
Table 3 reforming raw material oleum spirit desulfurating agent and CT-83 contrast
| Sequence number | The running numbering | Service temperature ℃ | Pressure | The stock oil sulphur content, μ g g -1 | The self-cleaning oil sulphur content, μ g g -1 |
| ??1 | Reforming raw material oleum spirit desulfurating agent | ????180 ????180 | Normal pressure | ????9.17 ????7.15 | ????0.10 ????0.13 |
| ??2 | ????CT-83 | ????180 ????180 | Normal pressure | ????9.17 ????7.15 | ????0.13 ????0.17 |
Claims (4)
1, a kind of reforming raw material oleum spirit desulfurating agent is to be carrier with the aluminum oxide, and nickel is active ingredient, and zinc oxide is promotor, it is characterized in that its composition proportioning (precentagewise meter) nickel content (in nickel oxide) is 10～70%; Zinc oxide content (in zinc oxide) is 10～60%; Alumina content is 5～40%.
2, a kind of preparation method of reforming raw material oleum spirit desulfurating agent adopts coprecipitation method, it is characterized in that it comprises processing step: A with nickel oxide, zinc oxide, and alumina material is by the above-mentioned per-cent ball grinder ball milling of packing into; B takes out raw materials mixed adding distilled water and rolls; The raw material that C will roll carries out granulation; The D particle carries out roasting; E carries out compressing tablet after mixing on tabletting machine; The F tablet activates under hydrogen-containing gas, and temperature control is as follows:
200±5℃——→340±5℃——→500±5℃
Activation in 2 hours 2 hours 2 hours is finished after naturally cooling is desulfurizing agent for reforming stock oil product of the present invention.
3, a kind of sweetening agent as claimed in claim 1 is characterized in that its composition proportioning (precentagewise meter) nickel content (in nickel oxide) 15～50%; Zinc oxide content (in zinc oxide) 10～45%; Alumina content 5～30%.
4, a kind of preparation method of sweetening agent as claimed in claim 2 is characterized in that nickel element adds with nickel oxide, nickelous carbonate, single nickel salt form, and preferably the form with nickel oxide or nickelous carbonate adds; Zinc element adds with zinc oxide, zinc carbonate, zinc nitrate form, preferably adds with zinc oxide, zinc carbonate form; Alumina catalyst support can add when precipitation nickelous carbonate or precipitation zinc carbonate, adds when being preferably in co-blended.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02112508 CN1358825A (en) | 2002-01-08 | 2002-01-08 | Reforming raw material oleum spirit desulfurating agent and preparation method |
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|---|---|---|---|
| CN 02112508 CN1358825A (en) | 2002-01-08 | 2002-01-08 | Reforming raw material oleum spirit desulfurating agent and preparation method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100363100C (en) * | 2004-02-16 | 2008-01-23 | 杨典明 | Desulfur catalyst |
| CN100389878C (en) * | 2004-10-29 | 2008-05-28 | 中国石油化工股份有限公司 | Method for preparing IIB metal-containing catalyst carrier |
| CN100586561C (en) * | 2003-07-14 | 2010-02-03 | 新日本石油株式会社 | Hydrodesulfurization catalyst and hydrodesulfurization process for gasoline fractions |
| CN102703119A (en) * | 2012-06-19 | 2012-10-03 | 沧州华海炼油化工有限责任公司 | Preparation method for base oil of aluminium product rolling oil |
| CN103240095A (en) * | 2012-02-14 | 2013-08-14 | 南京汇文新材料科技开发有限公司 | Methyl acetate hydrogenation catalyst and preparation method thereof |
| CN103316680A (en) * | 2012-03-20 | 2013-09-25 | 南京汇文新材料科技开发有限公司 | Preparation method and applications of ethyl acetate hydrogenation catalyst |
-
2002
- 2002-01-08 CN CN 02112508 patent/CN1358825A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100586561C (en) * | 2003-07-14 | 2010-02-03 | 新日本石油株式会社 | Hydrodesulfurization catalyst and hydrodesulfurization process for gasoline fractions |
| CN100363100C (en) * | 2004-02-16 | 2008-01-23 | 杨典明 | Desulfur catalyst |
| CN100389878C (en) * | 2004-10-29 | 2008-05-28 | 中国石油化工股份有限公司 | Method for preparing IIB metal-containing catalyst carrier |
| CN103240095A (en) * | 2012-02-14 | 2013-08-14 | 南京汇文新材料科技开发有限公司 | Methyl acetate hydrogenation catalyst and preparation method thereof |
| CN103316680A (en) * | 2012-03-20 | 2013-09-25 | 南京汇文新材料科技开发有限公司 | Preparation method and applications of ethyl acetate hydrogenation catalyst |
| CN102703119A (en) * | 2012-06-19 | 2012-10-03 | 沧州华海炼油化工有限责任公司 | Preparation method for base oil of aluminium product rolling oil |
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