CN1045120A - The method for transformation of hydrocarbon raw material - Google Patents
The method for transformation of hydrocarbon raw material Download PDFInfo
- Publication number
- CN1045120A CN1045120A CN90100978A CN90100978A CN1045120A CN 1045120 A CN1045120 A CN 1045120A CN 90100978 A CN90100978 A CN 90100978A CN 90100978 A CN90100978 A CN 90100978A CN 1045120 A CN1045120 A CN 1045120A
- Authority
- CN
- China
- Prior art keywords
- raw material
- zeolite
- described method
- catalyst
- aperture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/10—Catalytic reforming with moving catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/16—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "moving bed" method
Abstract
The method that such as gas oil straight run hydrocarbon feed is transformed, this method comprise that raw material is that the zeolite catalyst moving-bed of the zeolite of 0.3-0.7nm contacts being higher than under 480 ℃ the temperature with containing the aperture, is less than 10 seconds duration of contact.
Description
The present invention relates to the method for transformation of hydrocarbon raw material.
US4171257 has described a kind of by the crystalline aluminosilicate catalyst of raw material and ZSM-5 is contacted with raising hydrocarbon raw material method for quality under the pressure that are lower than 14 crust, 260 to 427 ℃ temperature and 0.1-151/l hour space velocity.The content of nitrogenous compound calculates with nitrogen and must be less than 5ppm w in the raw material such as boiling range is 230-437 ℃ gas oil.Upgraded product comprises alkenes such as propylene.
Compare with lower paraffin hydrocarbons, the reactivity of alkene makes them be suitable for further being converted into other product, so preferably produce alkene.Yet the shortcoming of aforesaid method is that must carry out strict denitrification to initial feed earlier handles, to avoid rapid catalyst deactivation.
Also can know by EP-B-131986 and US3758403, can select for use the alumina silicate catalyst mixture of forming by wide aperture crystal aluminum silicate regarding and narrow aperture silicate such as ZSM-5 to produce gasoline.Can be to the C that is obtained
3With C
4Olefin by-products is carried out alkylation and is handled to improve the overall yield of gasoline.The space velocity that is adopted in the embodiment that provides and other condition show to use to have the longer catalyzer fixed-bed reactor of duration of contact.
Below discovery be wonderful: adopting certain zeolite catalyst and making raw material with catalyzer at high temperature carries out under the situation of short-time contact, can be at the alkene that nitrogen content is required acquisition higher yields under the not too strict condition.In addition, be surprisingly found out that also that this conversion process is applicable to the product that also can obtain the enrichment light alkene than the straight run hydrocarbon feed of heavy thus.
Therefore, the invention provides a kind of making and contain the method that some transforms at the straight run hydrocarbon feed of 330 ℃ of following ebullient hydrocarbon at least, this method comprises that making raw material is 0.3-0.7mm with containing the aperture, preferably the zeolite catalyst moving-bed of 0.5-0.7mm contacts being higher than under 480 ℃ the temperature, is less than 10 seconds duration of contact.
Raw material and zeolite catalyst do not reach 10 seconds time.Suitable short contacting time is 0.1 second.If be 0.2-6 second the duration of contact of raw material and zeolite catalyst in the method that is adopted, can obtain good result.
Temperature is higher between the reaction period.High temperature and short contacting time this combines to make and is converted into the conversion of olefines rate and improves just.Temperature range is preferably 500-900 ℃, is good with 550-850 ℃ especially.
It is 0.3 to 0.7mm zeolite that zeolite catalyst can contain one or more apertures.This catalyzer also should contain the refractory oxide as jointing material.Suitable refractory oxide comprises aluminum oxide, silicon-dioxide, silica-alumina, magnesium oxide, titanium dioxide, zirconium white and their mixture.Be good with aluminum oxide especially wherein.The weight ratio of refractory oxide and zeolite is preferably 10: 90 to 90: 10, preferably 50: 50 to 85: 15.Catalyzer can also contain up to about 40%(heavy again) the aperture greater than the zeolite of 0.7nm.The suitable example of this class zeolite comprises faujasite, zeolite beta, zeolite omega, especially X zeolite and Y.It is 0.3 to 0.7nm zeolite that zeolite catalyst preferably only contains the aperture basically.
Used this term of zeolite of this specification sheets can not be regarded as only comprising crystalline sour aluminium.This term also comprises crystalline silicon-dioxide (silicalite), aluminosilicophosphate (SAPO), silicochromium hydrochlorate, silicic acid gallium, ferric metasilicate, aluminum phosphate (ALPO), silicoaluminate titanium (TASO), borosilicate, phosphorus titanium aluminate (TAPO) and silicoaluminate iron.
Be applicable to method of the present invention, and the aperture is that the example of 0.3 to 0.7nm zeolite comprises SAPO-4 and the SAPO-11 that is disclosed in US-A-4440871, be disclosed in the ALPO-11 of US-A-4310440, be disclosed in the TAPO-11 of US-A-4500651, be disclosed in the TASO-45 of EP-A-229295, be disclosed in just like the borosilicate among the US-A-4254297, and pure aluminium silicate such as erionite, ferrierite, Q and ZSM-type zeolite such as ZSM-5, ZSM-11, ZSM-12, ZSM-35, ZSZSM-23 and ZSM-38.Zeolite should be selected from crystalline metal silicate with ZSM-5 structure, ferrierite, erionite and composition thereof.Suitable example with crystalline metal silicate of ZSM-5 structure is to be disclosed in just like the pure aluminium silicate among the GB-B-2110559, silicic acid gallium, ferric metasilicate, scandium silicate and/or silicic acid rhodium.
During the preparation zeolite, in the zeolite of making, exist a large amount of alkalimetal oxides usually.Preferably with methods known in the art such as ion exchange method, thereby also visual concrete lazy condition is carried out calcination to remove the zeolite that contained basic metal obtains to be its hydrogen form subsequently.The zeolite that is used for the inventive method preferably is its hydrogen form basically.
The pressure that method of the present invention adopted can change in wide region.Yet this pressure preferably makes raw material exist with its gas phase form basically under main temperature or enters gas phase by contacting with catalyzer.Be convenient to reach the short contacting time of imagination like this.So, should adopt lower pressure.So just needn't adopt expensive compressor and high pressure vessel and miscellaneous equipment, be favourable therefore.Suitable pressure range is 1 to 10 crust.Can select pressure below atmospheric pressure for use, but had better not do like this.Under atmospheric pressure operating in is favourable economically.Other gaseous matter existence such as steam and/or nitrogen also can be arranged during conversion.
Method of the present invention is carried out in moving-bed.Beds can move up and down.When bed moved up, this method and FCC process were similar a bit.
In the method, on catalyzer, there are some coke to generate.So, should make catalyst regeneration.Preferably at catalyzer with after raw material contacts, use the oxidizing gas such as air to handle catalyzer, make its regeneration.Especially be good to adopt the cyclic regeneration method similar to the renovation process that adopted in the fluid catalytic cracking process.
If the speed that coke generates is not too fast, can design a kind of residence time of wherein granules of catalyst in reaction zone than the method for the residence time of raw material in reaction zone for length.Certainly to be less than for 10 seconds the duration of contact between raw material and the catalyzer.Usually be consistent with the residence time of raw material this duration of contact.The residence time of catalyzer is preferably 1-20 times of residence time of raw material.
The catalyst/feed weight ratio can in very large range change, for example, and can be up to 150kg catalyzer/1kg raw material or even higher.Preferably 20～100: 1.
The raw material that transforms with method of the present invention will contain the hydrocarbon that boiling point is at least 330 ℃.Therefore, do not comprise petroleum cuts lighter such as petroleum naphtha and kerosene.Preferably raw material has such boiling range, promptly has at least the 50%(heavy) raw material be 330 ℃ of following ebullient.Suitable raw material comprises reduced pressure distillate, long residuum, de-asphalting residual oil, alkane charging and can satisfy the normal pressure distillate such as gas oil that boiling range requires.The most handy gas oil of raw material or vacuum gas oil.After these raw materials are handled through the inventive method, just can obtain to have the very gas oil and the gas fraction that is rich in alkene of low pour point.
Compare with the described method of US4171257, one of advantage of the present invention is to select for use nitrogen content not influence activity of such catalysts basically greater than the raw material of 5ppmw.In suitable raw material, nitrogen content calculates with nitrogen can be greater than 10ppmw, even can be 1000ppmw or higher numerical value.
Further describe the present invention below with reference to embodiment.
Embodiment
The used charging of present embodiment is the gas oil with following properties:
Initial boiling point ℃ 213
20%(is heavy) 331
50%(is heavy) 379
90%(is heavy) 421
Full boiling point 448
Pour point ℃ 19.5
Flash-point ℃ 147
Carbon %(is heavy) 86.6
Hydrogen %(is heavy) 13.1
Sulphur %(is heavy) 0.3
Nitrogen ppmw 330
Place a downflow reactor to handle gas oil, feedstream and median size are the granules of catalyst of 74 μ m and flow downward with flowing in reactor.Selected catalyzer is 1: 3 for the ZSM-5(ZSM-5/ alumina weight ratio that exists with hydrogen form in alumina host).All experiments are all under atmospheric pressure carried out.Other operational condition and experimental result are as shown in the table.
Table 1
Operational condition:
Temperature of reactor ℃ 576
Catalyst oil is than g/g 124
Duration of contact, S 1.8
Product %(weight) be benchmark in the charging
C
11.9
C
2=1.4
C
211.3
C
3=3.8
C
325.4
C
4=3.3
C
412.2
C
5-221 ℃ 15.3
221-370 ℃ 12.59
370+ ℃ 1.1
Coke 11.1
By The above results as can be seen, a large amount of gaseous product are ethylenic unsaturated material.
Claims (10)
1, a kind of making contains the method that some transforms at the straight run hydrocarbon feed of 330 times ebullient hydrocarbon at least, and this method comprises that making raw material is that the zeolite catalyst moving-bed of 0.3-0.7nm zeolite contacts being higher than under 480 ℃ the temperature with containing the aperture, contacts at least 10 seconds.
2, in accordance with the method for claim 1, wherein raw material contacted for 0.2 to 6 second with zeolite catalyst.
3, according to claim 1 or 2 described methods, wherein temperature is 550-850 ℃.
4, according to any one described method among the claim 1-3, the aperture of its mesolite is 0.5 to 0.7nm.
5, according to any one described method among the claim 1-4, its mesolite is selected from crystalline metal silicate with ZSM-5 structure, ferrierite, erionite and composition thereof.
6, according to any one described method among the claim 1-5, wherein zeolite exists with its hydrogen form basically.
7, according to each described method among the claim 1-6, wherein pressure is the 1-10 crust.
8, according to any one described method among the claim 1-7, wherein the catalyst/feed weight ratio is 20～100: 1.
9, according to any one described method among the claim 1-8, wherein raw material is a gas oil.
10, a kind of hydrocarbon product or its cut of using the described method acquisition of above-mentioned any one claim.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8904408.5 | 1989-02-27 | ||
| GB898904408A GB8904408D0 (en) | 1989-02-27 | 1989-02-27 | Process for the conversion of a hydrocarbonaceous feedstock |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1045120A true CN1045120A (en) | 1990-09-05 |
| CN1019981C CN1019981C (en) | 1993-03-03 |
Family
ID=10652368
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90100978A Expired - Fee Related CN1019981C (en) | 1989-02-27 | 1990-02-26 | Process for conversion of hydrocarbonaceous feedstock |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0385538B1 (en) |
| JP (1) | JPH02276888A (en) |
| KR (1) | KR910015689A (en) |
| CN (1) | CN1019981C (en) |
| AU (1) | AU628929B2 (en) |
| BR (1) | BR9000880A (en) |
| CA (1) | CA2009986A1 (en) |
| DE (1) | DE69009234T2 (en) |
| ES (1) | ES2056362T3 (en) |
| GB (1) | GB8904408D0 (en) |
| RU (1) | RU2017791C1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9026775D0 (en) * | 1990-12-10 | 1991-01-30 | Shell Int Research | Process for the preparation of an olefins-containing mixture of hydrocarbons |
| GB9114390D0 (en) * | 1991-07-03 | 1991-08-21 | Shell Int Research | Hydrocarbon conversion process and catalyst composition |
| US6222087B1 (en) | 1999-07-12 | 2001-04-24 | Mobil Oil Corporation | Catalytic production of light olefins rich in propylene |
| US6835863B2 (en) | 1999-07-12 | 2004-12-28 | Exxonmobil Oil Corporation | Catalytic production of light olefins from naphtha feed |
| EP1195424A1 (en) | 2000-10-05 | 2002-04-10 | ATOFINA Research | A process for cracking an olefin-rich hydrocarbon feedstock |
| DE102012006992A1 (en) * | 2012-04-05 | 2013-10-10 | Linde Aktiengesellschaft | Process for the separation of olefins with mild cleavage |
| WO2017109639A1 (en) | 2015-12-21 | 2017-06-29 | Sabic Global Technologies B.V. | Methods and systems for producing olefins and aromatics from coker naphtha |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3856659A (en) * | 1972-12-19 | 1974-12-24 | Mobil Oil Corp | Multiple reactor fcc system relying upon a dual cracking catalyst composition |
| US4514285A (en) * | 1983-03-23 | 1985-04-30 | Texaco Inc. | Catalytic cracking system |
| US4985136A (en) * | 1987-11-05 | 1991-01-15 | Bartholic David B | Ultra-short contact time fluidized catalytic cracking process |
| GB8814292D0 (en) * | 1988-06-16 | 1988-07-20 | Shell Int Research | Process for conversion of hydrocarbonaceous feedstock |
| ES2087073T3 (en) * | 1988-06-16 | 1996-07-16 | Shell Int Research | PROCEDURE FOR THE CONVERSION OF A HYDROCARBON FEEDING MATERIAL. |
| NL8801653A (en) * | 1988-06-29 | 1990-01-16 | Stork Kwant Bv | OPERATING SYSTEM. |
| GB8828206D0 (en) * | 1988-12-02 | 1989-01-05 | Shell Int Research | Process for conversion of hydrocarbonaceous feedstock |
-
1989
- 1989-02-27 GB GB898904408A patent/GB8904408D0/en active Pending
-
1990
- 1990-02-14 CA CA002009986A patent/CA2009986A1/en not_active Abandoned
- 1990-02-21 ES ES90200415T patent/ES2056362T3/en not_active Expired - Lifetime
- 1990-02-21 DE DE69009234T patent/DE69009234T2/en not_active Revoked
- 1990-02-21 EP EP90200415A patent/EP0385538B1/en not_active Revoked
- 1990-02-22 BR BR909000880A patent/BR9000880A/en not_active Application Discontinuation
- 1990-02-23 AU AU50149/90A patent/AU628929B2/en not_active Ceased
- 1990-02-23 JP JP2041386A patent/JPH02276888A/en active Pending
- 1990-02-26 CN CN90100978A patent/CN1019981C/en not_active Expired - Fee Related
- 1990-02-26 RU SU904743371A patent/RU2017791C1/en active
- 1990-02-26 KR KR1019900002434A patent/KR910015689A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE69009234D1 (en) | 1994-07-07 |
| AU5014990A (en) | 1990-08-30 |
| BR9000880A (en) | 1991-02-13 |
| RU2017791C1 (en) | 1994-08-15 |
| EP0385538B1 (en) | 1994-06-01 |
| ES2056362T3 (en) | 1994-10-01 |
| KR910015689A (en) | 1991-09-30 |
| GB8904408D0 (en) | 1989-04-12 |
| JPH02276888A (en) | 1990-11-13 |
| DE69009234T2 (en) | 1994-11-24 |
| CA2009986A1 (en) | 1990-08-27 |
| CN1019981C (en) | 1993-03-03 |
| AU628929B2 (en) | 1992-09-24 |
| EP0385538A1 (en) | 1990-09-05 |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |