CN87103035A - Desulfurizing agent for reforming stock oil - Google Patents
Desulfurizing agent for reforming stock oil Download PDFInfo
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- CN87103035A CN87103035A CN87103035.7A CN87103035A CN87103035A CN 87103035 A CN87103035 A CN 87103035A CN 87103035 A CN87103035 A CN 87103035A CN 87103035 A CN87103035 A CN 87103035A
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- desulfurizing agent
- stock oil
- reforming
- copper
- oil
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Abstract
Desulfurizing agent for reforming stock oil is used for the product that refining of petroleum industry removes trace sulfide in the oil product.The present invention makes active ingredient with copper, nickel.Kaolin is made carrier.Be specially adapted to remove Determination of Trace Sulfur residual in the upstream process in the fixed-bed desulfurization of reforming raw oil after pre-hydrogenation dehydration by evaporation operation, the sulphur content of stock oil is dropped to below the 0.5ppm, has desulphurizing activated height, long service life, raw material is extensive, cost is low, do not produce the characteristics such as material of " murder by poisoning " reforming catalyst, have positively effect improving catforming process efficient.
Description
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 active constituent with platinum, with rhenium or other component is two (many) metal reforming catalysts of auxiliary agent, because two (many) metal reforming catalysts are very sensitive to sulphur compound, as long as there is the Determination of Trace Sulfur compound to exist in the stock oil, will cause catalyzer " poisoning " and reduce activity and selectivity, cause the fluid yield to reduce and catalyzer shortening in work-ing life, cause shut-down when serious.Therefore will guarantee that catalytic reforming process carries out smoothly, the sulphur content that at first will satisfy stock oil is avoided two (many) metal reforming catalysts to lose activity because of the stock oil sulphur content is high and is caused idle cost less than below the 0.5PPM.
The desulfurizing agent for reforming stock oil that the present invention proposes is mainly used in the fixed-bed desulfurization of reforming raw oil after pre-hydrogenation dehydration by evaporation operation, removes trace sulfide residual in the upstream process, makes the stock oil sulphur content drop to the following product of 0.5PPm.
In this technical field, the reformer feed desulfurating agent that uses at present has by contained active constituent classification: to contain zinc as main desulfurizing agent, take nickeliferous as main desulfurizing agent, take cupric as main three classes such as desulfurizing agent. According to the report of prior art＜sulphur to " 3741 " bimetallic catalyst influence on system operation〉(catalytic reforming communication 1984. № 3 P68-80) described, when operating temperature is 180 ℃, use contains active component zinc " 0703 " desulfurizing agent can get certain effect, but desulfuration efficiency is low, difficult assurance sulfur content in oil products stably is controlled at below the 0.5PPM, and can produce ZnCl2" murder by poisoning " catalytic reforming catalyst. Again According to prior art＜the second stage of the project imported unit appended heterogeneous catalysis and adsorbent overview ()〉(1980.6.15.P3 of Shanghai Petrochem. General Plant) described, the ADS-11 desulfurizing agent that contains active component nickel of UOP's outlet, the feed oil sulfur content can be removed to below the 0.5PPm by 1PPm, in 1 year service life, price is high and domestic out of stock. Again according to prior art＜U.S.P4113606〉described, the desulfurizing agent that contains active ingredient copper can be used for this process, but does not report the copper wastage of its desulfurization level and desulfurizing agent.
Problem in view of above-mentioned prior art existence, the objective of the invention is: invent a kind of for the fixed-bed desulfurization of reformer feed oil after pre-hydrogenation dehydration by evaporation operation, can remove the desulfurizing agent of residual minim sulfide in the upstream process, it can make the feedstock oil sulfur content drop to below the 0.5PPm, desulphurizing activated good characteristic, the while is not produced the material of " murder by poisoning " reforming catalyst. The manufacturing process of this desulfurizing agent is simple, and in 2 years service life, raw material is easy to get, and cost is low.
Desulfurizing agent for reforming stock oil of the present invention is to be carrier with kaolin, and copper, nickel or molybdenum are active ingredient, after mixing with blending method by a certain percentage, and through extruded moulding, drying, the product that makes after the roasting.
The proportioning of desulfurizing agent for reforming stock oil of the present invention (precentagewise meter) copper content (in cupric oxide) is 25-70%, is preferably in 30-55%; Nickel content (in nickel oxide) is 5-30%, is preferably in 10-25%; Kaolin content is that 25-60% is preferably in 30-50%.The copper of this sweetening agent adds with cupric oxide, copper carbonate, copper sulfate, cuprous chloride form, preferably adds with cupric oxide or copper carbonate form.Nickel element adds with nickel oxide, nickelous carbonate, nickelous nitrate form, preferably adds with nickel oxide, nickelous carbonate form, and carrier kaolin can add when precipitation copper carbonate or precipitation nickelous carbonate, adds when being preferably in co-blended.
Desulfurizing agent for reforming stock oil manufacture method of the present invention is:
1. with above-mentioned cupric oxide (copper carbonate, copper sulfate, cuprous chloride), nickel oxide (nickelous carbonate, nickelous nitrate).Materials such as kaolin are by the certain percentage ball grinder ball milling of packing into.
2. take out raw materials mixed and add the distilled water kneading.
3. kneaded raw material is carried out extrusion on banded extruder, the extruding specification is 1.2 millimeters strips of φ.
4. integer after the extrusion.300～350 rev/mins of rotating speeds, 10～15 minutes time.
5. airing, oven dry then in 24 hours after the integer.
6. will dry product activates under following condition:
Activation is finished after naturally cooling is desulfurizing agent for reforming stock oil product of the present invention.
The product physicals:
Specific surface: 40-50 rice
2/ gram; Pore volume: 0.22-0.24 milliliter/gram;
Intensity: the 3-5 kilogram/; 1.2 millimeters of particle diameter: φ.
Product is formed:
Desulfurizing agent for reforming stock oil of the present invention will reduce earlier in use.Condition is: 300 ± 5 ℃ of temperature; Time is more than 12 hours; Normal pressure; Medium H
2+ N
2Or H
2+ H
2O steam; Density of hydrogen 1-20%.
Desulfurizing agent for reforming stock oil working conditions of the present invention is:
Service temperature: 100-200 ℃
Working pressure: 0-15Kgf/cm
2
Liquid air speed: 0-12h
-1
Desulfurizing agent for reforming stock oil of the present invention, in the fixed-bed desulfurization of reforming raw oil after pre-hydrogenation dehydration by evaporation operation, result of use is will be removed to below the 0.5PPm about stock oil sulfur-bearing 1PPM, has any sweetening agent desulfuration efficiency height that uses than existing, activity is good, does not produce the material of " murder by poisoning " catalyzer, 2 years work-ing life, raw material is extensive, the feature that cost is low.
The embodiment of the invention (precentagewise meter)
Example one: cupric oxide: nickel oxide: kaolin=25: 30: 45
Example two: cupric oxide: nickel oxide: kaolin=35: 5: 60
Example three: cupric oxide: nickel oxide: kaolin=50: 25: 25
Example four: cupric oxide: nickel oxide: kaolin=55: 10: 35
Example five: cupric oxide: nickel oxide: kaolin=45: 25: 30
Example six: cupric oxide: nickel oxide: kaolin=70: 5: 25
Example seven: cupric oxide: nickel oxide: kaolin=30: 20: 50
Most preferred embodiment: cupric oxide: nickel oxide: kaolin=45: 20: 35
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 that the desulfurizing agent for reforming stock oil desulfuration efficiency is than nickeliferous ADS-11 sweetening agent height.
Table 2 shows that the desulfurizing agent for reforming stock oil desulfuration efficiency is than zinciferous 0703 sweetening agent height.
Table 3, desulfuration efficiency illustrates that still more than 95% the sweetening agent life-span is long when showing desulfurizing agent for reforming stock oil sulfur capacity 9%.
Table 4 shows that the characteristic that desulfurizing agent for reforming stock oil has a good organic sulfide removal increases with increase in temperature efficient.
Annotate: " stock oil " hurdle: 1 is the oil product before the pre-hydrogenation dehydration by evaporation; 2 for mainly containing the oil product of organosulfur; 3 for mainly containing the oil product of organosulfur, and the sweet oil sulphur content is higher slightly during preparation.
Claims (5)
1, a kind of desulfurizing agent for reforming stock oil of making as raw material by copper, nickel, kaolin, it is characterized in that, copper is with cupric oxide or copper carbonate or copper sulfate or cuprous chloride form, and nickel is with nickel oxide or nickelous carbonate or nickelous nitrate form, and kaolin is desulfurizing agent for reforming stock oil for the product of china clay blend preparation.
It is characterized in that according to the described desulfurizing agent for reforming stock oil of claim 1 that 2, copper is cupric oxide or copper carbonate, nickel is nickel oxide or nickelous carbonate, and kaolin is ceramics factory's china clay of trioxygen-containingization two aluminium and silicon-dioxide.
3, according to the described desulfurizing agent for reforming stock oil of claim 2, it is characterized in that:
Cupric oxide or copper carbonate: nickel oxide or nickelous carbonate: china clay=25-70: 5-30: 25-60(per-cent).
4, according to the described desulfurizing agent for reforming stock oil of claim 3, it is characterized in that: better formula is
Cupric oxide or copper carbonate: nickel oxide or nickelous carbonate: china clay=30-55: 10-25: 30-50(per-cent).
5,, it is characterized in that best proportioning is: cupric oxide: nickel oxide: china clay=45: 20: 35(per-cent) according to claim 1,2,3,4 described desulfurizing agent for reforming stock oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87103035.7A CN1003520B (en) | 1987-09-10 | 1987-09-10 | Desulphurizer for reforming raw oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87103035.7A CN1003520B (en) | 1987-09-10 | 1987-09-10 | Desulphurizer for reforming raw oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87103035A true CN87103035A (en) | 1988-03-02 |
| CN1003520B CN1003520B (en) | 1989-03-08 |
Family
ID=4814244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87103035.7A Expired CN1003520B (en) | 1987-09-10 | 1987-09-10 | Desulphurizer for reforming raw oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1003520B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382199B (en) * | 1999-12-14 | 2010-11-24 | 中国石油化工股份有限公司 | Desulfurization process and bimetallic sorbent systems for same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7051532B2 (en) * | 2003-10-17 | 2006-05-30 | General Electric Company | Methods and apparatus for film cooling gas turbine engine combustors |
-
1987
- 1987-09-10 CN CN87103035.7A patent/CN1003520B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382199B (en) * | 1999-12-14 | 2010-11-24 | 中国石油化工股份有限公司 | Desulfurization process and bimetallic sorbent systems for same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1003520B (en) | 1989-03-08 |
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