CN1041711A - Has improved optionally cobalt fischer-tropsch catalysts - Google Patents
Has improved optionally cobalt fischer-tropsch catalysts Download PDFInfo
- Publication number
- CN1041711A CN1041711A CN88107031A CN88107031A CN1041711A CN 1041711 A CN1041711 A CN 1041711A CN 88107031 A CN88107031 A CN 88107031A CN 88107031 A CN88107031 A CN 88107031A CN 1041711 A CN1041711 A CN 1041711A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- acid extraction
- catalyzer
- cobalt
- treated
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of cobalt fischer-tropsch catalysts of LZ-210 carrier steam-treated, acid extraction of application enhancements.This kind new catalyst system shows to have improved selectivity of product under the F-T synthesis reaction condition, and its evidence is that methane production descends C
5 +Yield increases with olefin yield and increases.
Description
The field that the present invention relates to is the cobalt fischer-tropsch catalysts that makes up with a kind of improved molecular sieve carrier.
In industrial fischer-tropsch is synthetic, general preferred employing be iron fischer-tropsch (F-T) catalyzer rather than cobalt-base catalyst, iron catalyst is the F-T synthetic catalyst of industrial unique use at present.
In F-T synthesis reaction, cobalt catalyst is used for synthetic gas (CO+H
2The advantage of conversion gas mixture) is active higher and higher to the selectivity that generates motor spirit, but shortcoming is that their institute's inherent production excessive methane (this is undesirable product) and the paraffin of product are too high.If can find a kind of stable F-T catalyzer, it can reduce methane-generated quantity, can increase C again
+ 5Product yield, and improve wherein olefin(e) centent, particularly C
5The olefin(e) centent of boiling range will be a significant improvement.
Existing a large amount of about with the prior art of the Fischer-Tropsch catalyst metal of molecular sieve component combination.The nearest prior art relevant with the present invention is to be presented to the prior art of quoting in people's such as J.A.Rabo No. 4,652,538, United States Patent (USP) and this patent.
R.B.Anderson shows " The Fischer-Tropsch Synthisis ", Academic Press, and address Orlando, FL 1984, has made fabulous summary for the cobalt fischer-tropsch catalysts of delivering in the past.In this part summary, promotor and catalyzer that former studies is crossed have been enumerated, comprising investigation for use Mn and Zn promotor.Below listed be the summary of the data of use Mn related in this article and Zr promotor.Fischer and Koch point out that the effect that Mn is added in a kind of cobalt-diatomite catalyzer is to make products distribution shift to heavier cut product, and this result with catalyzer gained of the present invention is similar.What Eidus and Bulanova did studies show that, adds ZrO in catalyzer of the same type
2Also obtain similar effect, but the present inventor with ZrO
2Adding is not observed this kind effect during by the promoted Co/TC-123 catalyst system of Mn.As far as we know, so far also nobody reported that application Mn and Zr united promoted catalyzer.
Dent, A.L. and Lin, M. be at Adv.Chem.Ser.178, reported in 47(1979) Mn is added in cobalt-aluminium oxide catalyst, can increase the olefin(e) centent in the product, and this and wes' data are consistent.
The applicant noticed about unique prior art of the stability of improving cobalt F-T catalyzer with Zr, was exactly that Eidus and Bulanova are reported in russian patent 150, No. 152 (on September 26th, 1962, November 27 1954 applying date).In this research work, use Zr to substitute thorium, to reduce this catalyzer to superheated susceptibility.
The invention relates to a kind of cobalt fischer-tropsch catalysts/combination of molecular sieve, wherein added a kind of molecular sieve of development newly, this molecular sieve has the improved performance higher than previously known molecular sieve carrier as support of the catalyst the time.
Have found that resulting this catalyzer has good selectivity of product and high stability, its evidence is that methane production is less, C
+ 5Yield is higher, and olefin yield increases, and catalyst life is longer.
The present inventor finds, has a kind of new carrier based on molecular sieve can reduce undesirable methane production with the cobalt fischer-tropsch catalysts of its combination widely.The minimizing of this kind methane production is because products distribution is shifted to the heavier product obtain of more wishing of cut causes.Observing has increased the product that is higher than the motor spirit boiling range significantly in the product of being produced, but this can not think a kind of shortcoming, because these products than last running are easy to be processed into hydrogenolysis the product of motor spirit boiling range.This molecular sieve carrier role is to reduce the hydrogenation ability of cobalt catalyst, promotes the chainpropagation of hydrocarbon chain terminal.With the consistent part of this theory is fischer-tropsch synthesis product, especially C
5The olefin(e) centent of boiling range increases, thereby improves the value of product.
The molecular sieve carrier called after TC-123 that the present invention is used, it is a kind of at United States Patent (USP) the 4th, 503,023 and 4,610, disclosed molecular sieve steam-treated, the acid extraction form that is called LZ-210 is formed in No. 856.Implementing known best way of the present invention is to use SiO
2/ Al
2O
3Than be 8.0 or above LZ-210 as initiator.The preferred method that preparation is used for LZ-210 molecular sieve of the present invention by Staniulis with this patent common that transfer the possession of, simultaneously apply for and the series number patent that awaits the reply open.This method comprises carries out a kind of LZ-210 secondary synthesis step with a kind of Y zeolite, and does not need to carry out a kind of follow-up ammonium ion exchange step.This kind material can be carried out ammonium ion exchange then and in 100% water vapor, carry out 1 hour steam-treated under 750 ℃, and then in 3M HCl solution, under refluxad use acid extraction 3 hours.Resulting product has following character: SiO
2/ Al
2O
3=200, surface area (lpt.BETo=800m
2/ g), X-ray a
0=24.260.
Micropore with this carrier fills with a kind of solution then, for example contains Co(NO
3)
2With a kind of Mn(NO
3)
4The ethylene glycol of promotor, water or (second) alcohol, its consumption are to make the theoretical content of Co and Mn reach Co=8.2%, Mn=1.6%.In the present invention narrated about improved content, the method for silica-bonded and moulding was not generally thought particularly important.
CHARACTERISTICS IDENTIFICATION to described catalyzer shows, is to be encapsulated in the secondary microvoid structure of this kind TC-123 molecular sieve as the cobalt oxide of promotor, and these micropores are handled by steam-treated and acid extraction and produced.These secondary micropores help to make cobalt granule to become desired specific size and keep this size, so that reach high reactivity and selectivity, and can also allow synthetic gas and reaction product diffuse through a microvoid structure of zeolite simultaneously.
The present invention has also narrated the application of the new catalyst system of the LZ-210 carrier that will contain cobalt and a kind of usefulness steam-treated and acid extraction as a kind of Fischer-Tropsch catalyst.
Promotor when using a kind of suitable Fischer-Tropsch catalyst for example behind Mn oxide compound, Zirconium oxide and their composition, can have and use catalyst system of the present invention excellently most.
Example
Though above invention has been described, but can further understand details of the present invention by following example, these examples are to be used for explanation for the promoted cobalt fischer-tropsch catalysts of a kind of Mn, use LZ-210 molecular sieve carrier a kind of steam-treated, acid extraction, when comparing, can obtain better result with the same catalyst that the UHP-Y molecular sieve that adopts known acid extraction (No. 4652538, people's such as No. 4401556, people's such as Bezman United States Patent (USP) and Rabo United States Patent (USP)) is made carrier.
Following each example same catalyst that to be the Fischer-Tropsch catalyst that will use promoted and UHP-Y acid extraction of manganese to make carrier make carrier with the LZ-210 molecular sieve of the acid extraction of using a kind of steam-treated compares.
These two kinds of catalyzer all are with identical preparation process, and operate at the same terms.
The example I
This Preparation of catalysts method is as follows: with the anhydrous TC-123 of 100.0g 7.21g Mn(NO
3)
2XH O, 55.8g Co(NO
3)
2The warm solution filling micropore of 6H O in 48.0g ethylene glycol.By following step dry and in air this catalyzer of roasting: 100 ℃ 10 hours, be warming up to 200 ℃ with 0.5 hour, kept 0.5 hour at 200 ℃, be warming up to 450 ℃ with 1.25 hours, 450 ℃ of maintenances 4 hours.The gained powder is become 1/8 inch the bar of extruding with silica-bonded and extruding, 110 ℃ of dried overnight, subsequently 250 ℃ of roastings 2 hours.Raw materials used with catalyzer is benchmark, calculates each component percentage to be: Co=8.2, Mn=1.6, silica binder=15%, TC-123=72.1.
The 80ml catalyst samples is contained in the Berty reactor, uses H under with 300 pounds/square inch gauge at 350 ℃
2Handled 18 hours, and at 220 ℃ and H
2: CO=1: 1 synthetic gas contact.240 ℃ with 260 ℃ with at different pressure and H
2: under the condition of CO ratio this catalyzer is tested.The gained test-results is listed in table 1.
The example II
Prepare another kind of catalyzer by the described same procedure of example I, but the UHP-Y molecular sieve of using acid extraction replaces the TC-123 molecular sieve in the example I.Same way as comparative catalyst's sample by the example I is tested, and the result also lists in table 1.
Table 1
The comparison of Co/Mn F-T catalyzer
Instance number I II
The UHP-Y of catalytic carrier TC-123 acid extraction
Transformation efficiency (H
2+ CO) 47.8 42.8
CH
43.3 5.3
C
2-C
47.8 9.7
C
5-350°F 21.4 23.0
350-650°F 29.0 31.5
650°F 38.6 30.4
C
+ 588.9 85.0
C
4Alkene/paraffinic hydrocarbon 3.7 2.1
Condition: 240 ℃, 1: 1 H
2: CO, 300 pounds/square inch gauge, 300GHSV(gas hourly space velocity)
Compare with the catalyzer of making carrier with UHP-Y, the catalyzer of making carrier with TC-123 shows and has reduced methane and C significantly
2-C
4Output, simultaneously both synthetic gas transformation efficiencys are close or the former is higher.C
1-C
4Cut reduces has increased more valuable C
+ 5Cut.As C
4Alkene/the paraffinic hydrocarbon of cut is than indicated, and is higher than the olefin product content of the catalyzer of using the UHP-Y carrier with the catalyzer of TC-123 carrier.
Though invention has been described by different specific exampless and embodiment,, should be realized that the present invention is not subjected to the restriction of these examples and embodiment, and can in the scope of claim of the present invention, implement.
Claims (16)
1, a kind of cobalt fischer-tropsch catalysts that uses LZ-210 molecular sieve steam-treated, acid extraction as carrier.
2, a kind of catalyzer by claim 1, the SiO of the LZ-210 of wherein said acid extraction
2/ Al
2O
3Than being 8.0 or higher.
3, a kind of catalyzer by claim 1, LZ-210 wherein are at 750 ℃ and use steam-treated 1 hour in 100% water vapors, use acid extraction subsequently again.
4, a kind of cobalt fischer-tropsch catalysts by claim 1 wherein makes up with a kind of suitable promotor of significant quantity.
5, a kind of cobalt 1 Fischer-Tropsch catalyst by claim 4, this promotor wherein is the Mn oxide compound.
6, the cobalt of claim 1 is stated from catalyzer on LZ-210 molecular sieve steam-treated, acid extraction and is used for that the catalysis fischer-tropsch is synthetic answers.
7, the cobalt of claim 6 is stated from the Application of Catalyst on LZ-210 molecular sieve steam-treated, acid extraction, the SiO of wherein said LZ-210 molecular sieve carrier
2/ Al
2O
3Than being 8.0 or higher.
8, the cobalt of claim 6 is stated from the Application of Catalyst on LZ-210 molecular sieve steam-treated, acid extraction, wherein said LZ-210 molecular sieve carrier in 100% water vapor, 750 ℃ with steam-treated 1 hour, use acid extraction subsequently again.
9, the cobalt of claim 6 is stated from catalyzer on LZ-210 molecular sieve steam-treated, acid extraction, after a kind of suitable promotor combination of significant quantity, is used for the catalysis F-T synthesis reaction.
10, the cobalt of claim 9 is stated from catalyzer on LZ-210 molecular sieve steam-treated, acid extraction, wherein said promotor is the Mn oxide compound, is used for the catalysis F-T synthesis reaction.
11, a kind of method of using synthetic gas feed stream enforcement F-T synthesis reaction, be included under the suitable F-T synthesis reaction condition, described feed stream is contacted with the catalyzer that contains cobalt and LZ-210 molecular sieve carrier steam-treated, acid extraction.
12, a kind of method by claim 1 enforcement F-T synthesis reaction, the SiO of wherein said LZ-210 molecular sieve carrier
2/ Al
2O
3Than being 8.0 or higher.
13, a kind of method by claim 1 enforcement F-T synthesis reaction, wherein said LZ-210 molecular sieve carrier in 100% water vapor, is used steam-treated 1 hour at 750 ℃, uses acid extraction subsequently again.
14, a kind of by claim 1, use the method that the synthetic gas feed stream is implemented F-T synthesis reaction, wherein this catalyzer also contains a kind of suitable promotor of significant quantity.
15, a kind of method by claim 14 enforcement F-T synthesis reaction, wherein this catalyzer also contains a kind of Mn oxide compound promotor.
16, a kind of method of using synthetic gas feed stream enforcement F-T synthesis reaction, comprising under suitable F-T synthesis reaction condition, with described feed stream with contain cobalt and LZ-210 molecular sieve carrier steam-treated, acid extraction and contact with the catalyzer of Mn combination of oxides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN88107031A CN1041711A (en) | 1988-09-16 | 1988-10-07 | Has improved optionally cobalt fischer-tropsch catalysts |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ZA886952A ZA886952B (en) | 1988-09-09 | 1988-09-16 | Cobalt fischer-tropsch catalysts having improved selectivity |
| CN88107031A CN1041711A (en) | 1988-09-16 | 1988-10-07 | Has improved optionally cobalt fischer-tropsch catalysts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1041711A true CN1041711A (en) | 1990-05-02 |
Family
ID=25742491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88107031A Pending CN1041711A (en) | 1988-09-16 | 1988-10-07 | Has improved optionally cobalt fischer-tropsch catalysts |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1041711A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103201030A (en) * | 2010-11-08 | 2013-07-10 | 国际壳牌研究有限公司 | Improvements relating to Fischer-Tropsch catalysts |
| CN105498798A (en) * | 2015-12-11 | 2016-04-20 | 中国科学院上海高等研究院 | Catalyst for directly converting synthesis gas into long-chain alkene by one-step method |
-
1988
- 1988-10-07 CN CN88107031A patent/CN1041711A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103201030A (en) * | 2010-11-08 | 2013-07-10 | 国际壳牌研究有限公司 | Improvements relating to Fischer-Tropsch catalysts |
| CN103201030B (en) * | 2010-11-08 | 2016-01-20 | 国际壳牌研究有限公司 | About the improvement of Fischer-Tropsch catalyst |
| US10155910B2 (en) | 2010-11-08 | 2018-12-18 | Shell Oil Company | Fischer-Tropsch catalysts |
| CN105498798A (en) * | 2015-12-11 | 2016-04-20 | 中国科学院上海高等研究院 | Catalyst for directly converting synthesis gas into long-chain alkene by one-step method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4514515A (en) | Process for manufacturing a catalyst comprising rhodium and at least one metal selected from the group consisting of tin, germanium and lead and the catalyst produced by the process | |
| US4735929A (en) | Catalytic composition for the isomerization of paraffinic hydrocarbons | |
| US4670472A (en) | Fischer-Tropsch process | |
| CN1044646A (en) | Method of dehydrogenating | |
| US4400576A (en) | Catalyst preparation | |
| DE1151082B (en) | Reforming catalyst | |
| EP0273091B1 (en) | Process for isomerizing xylene | |
| US4499195A (en) | Thermally stable mixed oxide gels | |
| US3668269A (en) | A process for disproportionating paraffinic hydrocarbons to yield products containing iso-paraffinic hydrocarbons | |
| JPH0629199B2 (en) | Method for isomerizing hydrocarbons | |
| DE1442850A1 (en) | Catalyst for the conversion of hydrocarbons | |
| US4469813A (en) | Process for the preparation of catalytically active cross-linked metal silicates | |
| CN1041711A (en) | Has improved optionally cobalt fischer-tropsch catalysts | |
| US3673267A (en) | Isomerization of cyclohexane in the presence of a mordenite catalyst | |
| US4309277A (en) | Conversion of hydrocarbons with a catalyst comprising an alumina-zeolite, a group VI-B metallic component and a group VIII metallic component | |
| JPH0529504B2 (en) | ||
| CN1052968C (en) | Akylation of benzene and ethylbenzene manufactured from ethylene | |
| CN1164360C (en) | Catalyst for hydrogenating Fischer-Tropsch synthetic wax and its prepn | |
| CN1079285C (en) | Catalyst for alkylation of benzene and ethylbenzene manufactured from ethylene | |
| EP0398416B1 (en) | Process for isomerising hydrocarbons | |
| CN1298684C (en) | Process for preparing octaene by butene oligomerization | |
| GB2151603A (en) | Modified clay | |
| US4587009A (en) | Hydrocarbon hydrogenation with thermally stable mixed titanium oxide gels | |
| EP0233382B1 (en) | Process for the preparation of liquid hydrocarbons | |
| CN1017313B (en) | Cobalt fischer-tropsch catalysts having improved selectivity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |