CN104549343A - Catalyst for preparing low-carbon olefin from synthesis gas as well as preparation method and application of catalyst - Google Patents
Catalyst for preparing low-carbon olefin from synthesis gas as well as preparation method and application of catalyst Download PDFInfo
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- CN104549343A CN104549343A CN201310512451.9A CN201310512451A CN104549343A CN 104549343 A CN104549343 A CN 104549343A CN 201310512451 A CN201310512451 A CN 201310512451A CN 104549343 A CN104549343 A CN 104549343A
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Abstract
The invention relates to a catalyst for preparing low-carbon olefin from synthesis gas as well as a preparation method and application of the catalyst, and aims at mainly solving the problems in a process of preparing the low-carbon olefin from the synthesis gas that the activity and the selectivity of the catalyst are low at a low temperature. The problems are solved very well by adopting the technical scheme that a Fischer-Tropsch synthesis catalyst is adopted and is prepared from the following components in percentage by weight: (1) 20%-80% of an active component; (2) 20%-80% of a carrier, wherein the carrier is selected from at least one of SiO2 and Al2O3; the active component is represented by the following formula according to an atomic ratio: Fe100AaBbKcOx, wherein A is at least one of Cu and Zn; B is at least one of Cr and Mo; the value range of a is 5-50; the value range of b is 5-150; and the value range of c is 0.1-5. The catalyst can be used for industrial production of preparing the low-carbon olefin from the synthesis gas.
Description
Technical field
The present invention relates to a kind of preparation of low carbon olefines by synthetic gas catalyst, preparation method and its usage.
Background technology
The low-carbon alkene being representative with ethene, propylene (alkene of carbon atom≤4) is the base stock of chemical industry, at present, the primary raw material of low-carbon alkene is petroleum hydrocarbon in the world, and wherein naphtha accounts for major part, also has alkane, hydrogenated diesel oil, part heavy wet goods.Domestic and international is raw material mainly with natural gas or light petroleum fraction, adopts steam cracking process in Ethylene Complex unit to produce low-carbon alkene.Steam cracking is the large power consumption device in petrochemical industry, and relies on non-renewable petroleum resources completely.Along with the day by day shortage of petroleum resources, be badly in need of finding alternate resources.So be then taken seriously with the research work of substitute gas oil producing olefinic hydrocarbons, some famous oil companies and scientific research institutions have all carried out the research and development of this respect in the world, and achieve achievement attracting people's attention.In the structure of current adjustment using energy source progressively to reduce the national economic development under the background of the dependence of petroleum-based energy, utilize the natural gas resource of China's rich reserves, by gas making producing synthesis gas (carbon monoxide and hydrogen mixed gas), be converted into the alkene of C2 ~ C4 again, in the long term, there is very high strategic importance.
Synthetic holography becomes the method for alkene to comprise indirect method and direct method, methanol decomposition preparing low-carbon olefins MTO technique with become gas via dimethyl ether preparing low-carbon olefins SDTO technique, first by synthesis gas synthesizing methanol or dimethyl ether, then become alkene by methyl alcohol or dimethyl ether conversion.
Fischer-Tropsch (Fascher-Tropsch) synthesis utilizes synthesis gas (main component is CO and H
2) under the effect of catalyst, synthesize the process of hydrocarbon, be an important channel of coal and natural gas indirect liquefaction.The method is invented by Germany scientist Frans Fischer and Hans Tropsch nineteen twenty-three, and namely heterogeneous catalysis hydrogenation occurs CO on metallic catalyst, generates based on the process of the mixture of linear paraffin and alkene.Germany has just carried out research and development in the twenties in last century, and achieves industrialization in 1936, closes after World War II because competing with petroleum industry economically; South Africa has abundant coal resources, but petroleum resources plaque is weary, and be subject to the restriction of international community's economy and political sanction for a long time, force its Development of Coal oils preparation industry technology, and built up in 1955 the coal-based F-T artificial oil factory (Sasol-1) that First production capacity is 25 ~ 400,000 tons of product/years.Twice world oil crisis of 1973 and 1979, cause world's crude oil price to fall and swing fluctuating, big rise and big fall, based on the consideration of Strategic Technology deposit, F-T synthetic technology arouses the interest of industrialized country again.1980 and nineteen eighty-two, South Africa Sasol company builds up again and two coal-based artificial oil factories of having gone into operation in succession.But plummeting of World oil price in 1986, has postponed the heavy industrialization process of F-T synthetic technology in other country.Since twentieth century nineties, petroleum resources are shortage and in poor quality increasingly, and coal and natural gas proved reserves but constantly increase simultaneously, and fischer-tropsch technologies causes extensive concern again, and Fiscber-Tropscb synthesis technology have also been obtained significant progress.Fischer-tropsch catalysts conventional at present, is divided into two large classes: ferrum-based catalyst and cobalt-base catalyst active component; And common synthesis technique is divided into two large classes from the words that synthesis condition angle is classified: high temperature fischer-tropsch synthesis technique and Low Temperature Fischer Tropsch synthesis technique; Synthesis technique is divided into three major types from the used reactor difference words of classifying: fixed bed fischer-tropsch synthesis process, fluid bed fischer-tropsch synthesis process (have early stage recirculating fluidized bed and developed out afterwards on recirculating fluidized bed basis fixed fluidized bed) and syrup state bed Fischer Tropsch synthesis technique.Fixed bed wherein and slurry bed system are generally applied to low temperature fischer-tropsch process, are used for the production of mink cell focus and wax, and fluid bed is then more suitable for the high temperature fischer-tropsch technique of the hydro carbons producing comparatively lightweight.
The object of present carbon-chemical synthesis hydro carbons is translated into the low-carbon alkene as basic chemical raw materials, and wherein ethene and propylene are the materials of current most worthy.And be that single step reaction generates object product by the direct preparing low-carbon olefins of synthesis gas, its technological process is simpler than indirect method, and economic evaluation is also more worthwhile.Last decade, causes concern by the direct synthesizing low-carbon alkene of synthesis gas.
By F-T synthesis, synthesis gas is converted into low-carbon alkene, except the impact by reaction process condition and thermodynamics and kinetics aspect, catalyst is then one of vital influence factor.Nineteen twenty-three Germany scientist Franz Fisher and Hans Tropsch has found the reaction of syngas catalytic conversion hydro carbons, therefore, the method being prepared hydro carbons by synthesis gas reaction is called Fiscber-Tropscb synthesis (Fischer-Tropsch synthesizes, and is called for short F-T synthesis) method, namely with CO and H
2react hydro carbons processed, byproduct water and CO
2.Nineteen fifty-five South Africa SASOL(South Africa Coal and Gas Corporation) to have built up take coal as the large-scale fixed bed F-T synthesizer of raw material, develop circulating fluidized bed technique subsequently, develop again fixed fluidized bed and slurry bed system technology recently.Nowadays, the coal year disposal ability of SASOL has reached 5,000 ten thousand, and the annual capacity of oil product and chemicals reaches 7,600,000 tons.The F-T synthesis reaction in past its objective is by synthesis gas synthetic fuel liquefied hydrocarbon, although the use of fluidization, ferrum-based catalyst and the interpolation of auxiliary agent, improve the yield of low-carbon alkene (C2-C4 alkene) to a certain extent, but yield of light olefins is still not high, only has 20-25%.
Mainly contained following several at present by preparing low-carbon olefin catalyst system and catalyzing.(1) improve the people such as F-T catalyst Dent and find that cobalt-base catalyst can be used for the synthesizing low-carbon alkene of high selectivity, as: Co-Cu/Al
2o
3, Co-Fe/SiO
2, Fe-Co/C, Co-Ni/MnO
2, the system such as Fe-Co alloy.Wherein better with the improvement FT catalyst result of Rule chemical company exploitation, at Fe-ZnO-K
2o catalyst adds the components such as Mn or Ti, adopts high gas circulation, reach CO conversion ratio 80%, selectivity of light olefin 70%; (2) Ultra-fine Particle Catalysts Venter etc. are obtained the high dispersive K-Fe-Mn catalyst of Activated Carbon Supported by carbonyl complex decomposition method, and catalyst has very high activity, C in product
2-C
4alkene accounts for 85-90%, and methane is other the unique products detected.The people such as Cupta utilize laser pyrolysis processes to prepare the Fe with catalytic activity
xsi
yc
zbe 40%, C Deng powder CO conversion ratio
2 =-C
4 =selectively reach 87%, only have a small amount of methane.The people such as Shanxi coalification institute Zhong Ping adopt the edman degradation Edman of organic salt complex successfully to develop and develop novel, to have practical background ultrafine particle Fe/Mn catalyst, and CO conversion ratio is greater than 95%, C
2 =-C
4 =/ C
2-C
4be greater than 80%.Beijing University of Chemical Technology Zhang Jingchang utilizes laser pyrolysis processes to prepare high degree of dispersion amorphous superfine iron powder and carbon dust, through solid phase reaction successfully obtained F-T synthesizing activity new species Fe
3c.Prepare with Fe
3c is the Fe-C of main body, the nanocatalysts such as Fe-C-Mn, Fe-C-Mn-K, and CO conversion ratio reaches 90%, and olefine selective reaches more than 80%; (3) people such as amorphous state synthetic catalyst Yokoyama uses amorphous state Fe
40ni
40p
16b
4compound, CO conversion ratio 50%, C
2-C
5hydrocarbon-selective is 65%, and crystalline-state catalyst mainly generates methane; (4) zeolite catalyst represents system the catalyst such as Co-A, Co-Y, Fe-Y, and the people such as Ballivet-Tketchenko obtain the iron catalyst of the high dispersive that zeolite supports, and selectivity of light olefin is quite high, and 88-98% is at C
2-C
4in scope, other iron catalysts supported as ZSM-5, mercerising, 13X zeolite also demonstrate similar behavior.But these catalyst are being prepared Repeatability, are being amplified and prepare in supervisor the difficulty run in various degree.
Summary of the invention
One of technical problem that the present invention solves is the problem that under preparation of low carbon olefines by synthetic gas in prior art (C2-C4 alkene) catalyst low temperature, activity and selectivity is low, a kind of preparation of low carbon olefines by synthetic gas catalyst is provided, this catalyst, for the synthesis of gas producing light olefins, has good low temperature active and selectivity of light olefin.Two of the technical problem that the present invention solves are to provide a kind of preparation method of the catalyst corresponding with one of technical solution problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation of low carbon olefines by synthetic gas catalyst, in catalyst weight percent, comprises following component:
The active component of (1) 20 ~ 80%;
The carrier of (2) 20 ~ 80%, carrier is selected from SiO
2or Al
2o
3in at least one;
Described active component can by following general formula with atomic ratio measuring: Fe
100a
ab
bk
co
x
Wherein A is at least one be selected from Cu or Zn;
B is at least one be selected from Cr or Mo;
The span of a is: 5 ~ 50;
The span of b is: 5-150;
The span of c is: 0.1 ~ 5;
X is for meeting the oxygen atom sum needed for other element valence.
In such scheme, the preferred version of catalyst is be also at least one be selected from Se and Te containing component D, D, and the atomic ratio of D and Fe is the span of d:100, d is 0.2-1; The preferable range of a is 10 ~ 40; The preferable range of b is: 20 ~ 120; The preferable range of c is: 0.5 ~ 3; The preferable range of d is 0.5-0.8.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the preparation method of catalyst comprises the following steps:
(1) soluble-salt containing component Fe, A and K is dissolved in deionized water wiring solution-forming
;
(2) soluble-salt containing B component is dissolved in deionized water wiring solution-forming
;
(3) by solution
add solution
middle formation mixture
;
(4) powder or colloidal sol that contain carrier are added mixture
, obtained mixture
;
(5) mixture is regulated with alkali
pH value to 8 ~ 10, the concentrated obtained slurry of heating;
(6) slurry drying obtains catalyst precursor;
(7) catalyst precursor obtains catalyst through roasting.
In technique scheme, after step (5) is concentrated, the slurry solid content of gained is 60 ~ 80 % by weight; The preferable range of step (6) baking temperature is 70 ~ 90 DEG C, and the preferable range of drying time is 5 ~ 40 hours; The preferable range of step (7) sintering temperature is 500 ~ 800 DEG C, and the preferable range of roasting time is 2 ~ 12 hours.
By described catalyst for the synthesis of gas reaction for preparing light olefins, be 220 ~ 280 DEG C in reaction temperature, reaction pressure is 0.5 ~ 2.5MPa, volume space velocity 1000-4000h
-1condition under, synthesis gas and described catalyst exposure react and generate low-carbon alkene.
The present invention, by adding various effective auxiliary agent, strengthens the adsorption activation of carbon monoxide and hydrogen, promotes the reduction of iron, can keep higher activity and selectivity of light olefin, can avoid carbon distribution problem when at high temperature reacting under lower reaction temperature.The present invention is simultaneously by adding
a race oxide, can promote the dispersion of active component oxide, and in catalyst reduction process, can fix active component better, makes it to keep good decentralization.
Adopt catalyst prepared by the present invention, at 250-350 DEG C, 0.5-2.5MPa, volume space velocity 1000-4000h
-1condition under react, CO conversion ratio >80%, C
2-C
4olefine selective >55%, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Get 118.27 grams of ferric nitrates, 0.17 gram of potassium nitrate and 12.25 grams of copper nitrates are dissolved in 100 ml waters and are made into certain density solution I, 47.7 grams of ammonium heptamolybdates are dissolved in 100 ml waters and obtain solution II, solution II is added in solution I and obtains mixture I, the Alumina gel being 25 % by weight by 120 grams of alumina contents adds mixture I and obtains mixture II by ammoniacal liquor adjust ph to 8, mixture II is placed in boiling water bath heating to be concentrated into solid content 55 % by weight and to obtain slurry, slurry is obtained catalyst precursor in 12 hours at 80 DEG C with the heated air drying that relative humidity is 90%, by catalyst precursor at 750 DEG C of roastings, 3 hours obtained catalyst, it consists of: 70%Fe
100mo
80cu
8k
0.5ox+30%Al
2o
3.Catalyst crushing and screening 20-40 order particle is stand-by.
[embodiment 2]
Get 118.3 grams of ferric nitrates, 17.1 gram zinc nitrate solution, 9.83 grams of nickel nitrates and 1.03 grams of potassium nitrate are dissolved in 100 ml waters and are made into certain density solution I, 52.6 grams of chromic nitrates and 0.15 gram of ammonium tellurate are dissolved in 100 ml waters and obtain solution II, solution II is added in solution I and obtains mixture I, the Ludox being 40% by 125 grams of siliconoxide mass content adds mixture I and obtains mixture II by ammoniacal liquor adjust ph to 9, mixture II is placed in boiling water bath heating to be concentrated into solid content 55 % by weight and to obtain slurry, slurry is obtained catalyst precursor in 5 hours at 90 DEG C with the heated air drying that relative humidity is 90%, by catalyst precursor at 650 DEG C of roastings, 5 hours obtained catalyst, it consists of: 50%Fe
100ni
10cr
45zn
17k
3te
0.2ox+50%SiO
2.Catalyst crushing and screening 20-40 order particle is stand-by.
[embodiment 3]
Get 54.2 grams of ferric nitrates, 0.17 gram of potassium nitrate and 5.61 grams of copper nitrates are dissolved in 100 ml waters and are made into certain density solution I, 0.17 gram of ammonium selenate and 19 grams of ammonium heptamolybdates are dissolved in 100 ml waters and obtain solution II, solution II is added in solution I and obtains mixture I, by 49.3 grams of siliconoxide mass content be 40% Ludox and 201.1 grams of quality of alumina content be 25% Alumina gel add mixture I and obtain mixture II by ammoniacal liquor adjust ph to 8, mixture II is placed in boiling water bath heating to be concentrated into solid content 55 % by weight and to obtain slurry, slurry is obtained catalyst precursor in 24 hours at 80 DEG C with the heated air drying that relative humidity is 90%, by catalyst precursor at 750 DEG C of roastings, 8 hours obtained catalyst, it consists of: 30%Fe
100mo
70cu
15k
1se
0.6o
x+ 70%Si
1al
3o
6.5.Catalyst crushing and screening 20-40 order particle is stand-by.
[embodiment 4]
Get 64.5 grams of ferric nitrates, 0.19 gram of potassium nitrate and 6.67 grams of copper nitrates are dissolved in 100 ml waters and are made into certain density solution I, 0.2 gram of ammonium selenate and 44.6 grams of chromic nitrates are dissolved in 100 ml waters and obtain solution II, solution II is added in solution I and obtains mixture I, by 49.3 grams of siliconoxide mass content be 40% Ludox and 201.1 grams of quality of alumina content be 25% Alumina gel add mixture I and obtain mixture II by ammoniacal liquor adjust ph to 8, mixture II is placed in boiling water bath heating to be concentrated into solid content 55 % by weight and to obtain slurry, slurry is obtained catalyst precursor in 24 hours at 80 DEG C with the heated air drying that relative humidity is 90%, by catalyst precursor at 750 DEG C of roastings, 8 hours obtained catalyst, it consists of: 30%Fe
100cr
70cu
15k
1se
0.6o
x+ 70%Si
1al
3o
6.5.Catalyst crushing and screening 20-40 order particle is stand-by.
[embodiment 5]
Get 54.4 grams of ferric nitrates, 0.17 gram of potassium nitrate and 5.63 grams of copper nitrates are dissolved in 100 ml waters and are made into certain density solution I, 19.2 grams of ammonium heptamolybdates are dissolved in 100 ml waters and obtain solution II, solution II is added in solution I and obtains mixture I, by 49.3 grams of siliconoxide mass content be 40% Ludox and 201.1 grams of quality of alumina content be 25% Alumina gel add mixture I and obtain mixture II by ammoniacal liquor adjust ph to 8, mixture II is placed in boiling water bath heating to be concentrated into solid content 55 % by weight and to obtain slurry, slurry is obtained catalyst precursor in 24 hours at 80 DEG C with the heated air drying that relative humidity is 90%, by catalyst precursor at 750 DEG C of roastings, 8 hours obtained catalyst, it consists of: 30%Fe
100mo
70cu
15k
1o
x+ 70%Si
1al
3o
6.5.Catalyst crushing and screening 20-40 order particle is stand-by.
[embodiment 6]
Get 54.2 grams of ferric nitrates, 0.17 gram of potassium nitrate and 5.61 grams of copper nitrates are dissolved in 100 ml waters and are made into certain density solution I, by 0.08 gram of ammonium selenate, 0.11 gram of ammonium tellurate and 19.1 grams of ammonium heptamolybdates are dissolved in 100 ml waters and obtain solution II, solution II is added in solution I and obtains mixture I, by 49.3 grams of siliconoxide mass content be 40% Ludox and 201.1 grams of quality of alumina content be 25% Alumina gel add mixture I and obtain mixture II by ammoniacal liquor adjust ph to 8, mixture II is placed in boiling water bath heating to be concentrated into solid content 55 % by weight and to obtain slurry, slurry is obtained catalyst precursor in 24 hours at 80 DEG C with the heated air drying that relative humidity is 90%, by catalyst precursor at 750 DEG C of roastings, 8 hours obtained catalyst, it consists of: 30%Fe
100mo
70cu
15k
1se
0.3te
0.3o
x+ 70%Si
1al
3o
6.5.Catalyst crushing and screening 20-40 order particle is stand-by.
[embodiment 7]
Get 58.9 grams of ferric nitrates, 0.17 gram of potassium nitrate and 6.1 grams of copper nitrates are dissolved in 100 ml waters and are made into certain density solution I, by 0.18 gram of ammonium selenate, 720.4 grams of chromic nitrates and 10.4 grams of ammonium heptamolybdates are dissolved in 100 ml waters and obtain solution II, solution II is added in solution I and obtains mixture I, by 49.3 grams of siliconoxide mass content be 40% Ludox and 201.1 grams of quality of alumina content be 25% Alumina gel add mixture I and obtain mixture II by ammoniacal liquor adjust ph to 8, mixture II is placed in boiling water bath heating to be concentrated into solid content 55 % by weight and to obtain slurry, slurry is obtained catalyst precursor in 24 hours at 80 DEG C with the heated air drying that relative humidity is 90%, by catalyst precursor at 750 DEG C of roastings, 8 hours obtained catalyst, it consists of: 30%Fe
100mo
35cr
35cu
15k
1se
0.6o
x+ 70%Si
1al
3o
6.5.Catalyst crushing and screening 20-40 order particle is stand-by.
[embodiment 8]
Get 54.2 grams of ferric nitrates, 0.16 gram of potassium nitrate, 2.3 grams of zinc nitrates and 3.74 grams of copper nitrates are dissolved in 100 ml waters and are made into certain density solution I, 0.17 gram of ammonium selenate and 19.1 grams of ammonium heptamolybdates are dissolved in 100 ml waters and obtain solution II, solution II is added in solution I and obtains mixture I, by 49.3 grams of siliconoxide mass content be 40% Ludox and 201.1 grams of quality of alumina content be 25% Alumina gel add mixture I and obtain mixture II by ammoniacal liquor adjust ph to 8, mixture II is placed in boiling water bath heating to be concentrated into solid content 55 % by weight and to obtain slurry, slurry is obtained catalyst precursor in 24 hours at 80 DEG C with the heated air drying that relative humidity is 90%, by catalyst precursor at 750 DEG C of roastings, 8 hours obtained catalyst, it consists of: 30%Fe
100mo
70cu
10zn
5k
1se
0.6o
x+ 70%Si
1al
3o
6.5.Catalyst crushing and screening 20-40 order particle is stand-by.
[embodiment 9]
Get 54.1 grams of ferric nitrates, 0.16 gram of potassium nitrate and 5.61 grams of copper nitrates are dissolved in 100 ml waters and are made into certain density solution I, 0.21 gram of ammonium tellurate and 19.1 grams of ammonium heptamolybdates are dissolved in 100 ml waters and obtain solution II, solution II is added in solution I and obtains mixture I, by 49.3 grams of siliconoxide mass content be 40% Ludox and 201.1 grams of quality of alumina content be 25% Alumina gel add mixture I and obtain mixture II by ammoniacal liquor adjust ph to 8, mixture II is placed in boiling water bath heating to be concentrated into solid content 55 % by weight and to obtain slurry, slurry is obtained catalyst precursor in 24 hours at 80 DEG C with the heated air drying that relative humidity is 90%, by catalyst precursor at 750 DEG C of roastings, 8 hours obtained catalyst, it consists of: 30%Fe
100mo
70cu
15k
1te
0.6o
x+ 70%Si
1al
3o
6.5.Catalyst crushing and screening 20-40 order particle is stand-by.
[embodiment 10]
Get 54.1 grams of ferric nitrates, 0.16 gram of potassium nitrate and 6.9 grams of zinc nitrates are dissolved in 100 ml waters and are made into certain density solution I, 0.17 gram of ammonium selenate and 19.1 grams of ammonium heptamolybdates are dissolved in 100 ml waters and obtain solution II, solution II is added in solution I and obtains mixture I, by 49.3 grams of siliconoxide mass content be 40% Ludox and 201.1 grams of quality of alumina content be 25% Alumina gel add mixture I and obtain mixture II by ammoniacal liquor adjust ph to 8, mixture II is placed in boiling water bath heating to be concentrated into solid content 55 % by weight and to obtain slurry, slurry is obtained catalyst precursor in 24 hours at 80 DEG C with the heated air drying that relative humidity is 90%, by catalyst precursor at 750 DEG C of roastings, 8 hours obtained catalyst, it consists of: 30%Fe
100mo
70zn
15k
1se
0.6o
x+ 70%Si
1al
3o
6.5.Catalyst crushing and screening 20-40 order particle is stand-by.
[embodiment 11]
Get 53.3 grams of ferric nitrates, 0.05 gram of potassium nitrate, 13.6 grams of zinc nitrates and 7 grams of copper nitrates are dissolved in 100 ml waters and are made into certain density solution I, by 0.35 gram of ammonium tellurate, 2.63 grams of chromic nitrates and 25.5 grams of ammonium heptamolybdates are dissolved in 100 ml waters and obtain solution II, solution II is added in solution I and obtains mixture I, by 67 grams of siliconoxide mass content be 40% Ludox and 134.4 grams of quality of alumina content be 25% Alumina gel add mixture I and obtain mixture II by ammoniacal liquor adjust ph to 8, mixture II is placed in boiling water bath heating to be concentrated into solid content 55 % by weight and to obtain slurry, slurry is obtained catalyst precursor in 36 hours at 75 DEG C with the heated air drying that relative humidity is 90%, by catalyst precursor at 600 DEG C of roastings, 10 hours obtained catalyst, it consists of: 40%Fe
100mo
95cr
5cu
19zn
30k
0.3te
1.0o
x+ 60%Si
2al
3o
8.5.Catalyst crushing and screening 20-40 order particle is stand-by.
[embodiment 12]
Get 88.7 grams of ferric nitrates, 0.2 gram of potassium nitrate, 2.26 grams of zinc nitrates and 15.3 grams of copper nitrates are dissolved in 100 ml waters and are made into certain density solution I, by 0.23 gram of ammonium tellurate, 0.14 gram of ammonium selenate, 7.89 grams of chromic nitrates and 44.7 grams of ammonium heptamolybdates are dissolved in 100 ml waters and obtain solution II, solution II is added in solution I and obtains mixture I, the Ludox being 40% by 87.5 grams of siliconoxide mass content adds mixture I and obtains mixture II by ammoniacal liquor adjust ph to 8, mixture II is placed in boiling water bath heating to be concentrated into solid content 55 % by weight and to obtain slurry, slurry is obtained catalyst precursor in 40 hours at 70 DEG C with the heated air drying that relative humidity is 90%, by catalyst precursor at 800 DEG C of roastings, 2 hours obtained catalyst, it consists of: 65%Fe
100mo
100cr
9cu
25zn
3k
0.8se
0.3te
0.4o
x+ 35%SiO
2.Catalyst crushing and screening 20-40 order particle is stand-by.
[embodiment 13]
Get 205.2 grams of ferric nitrates, 1.48 gram potassium nitrate, 17.4 grams of zinc nitrates and 3.54 grams of copper nitrates are dissolved in 100 ml waters and are made into certain density solution I, 0.67 gram of ammonium tellurate and 25.9 grams of ammonium heptamolybdates are dissolved in 100 ml waters and obtain solution II, solution II is added in solution I and obtains mixture I, by 33.8 grams of siliconoxide mass content be 40% Ludox and 45.9 grams of quality of alumina content be 25% Alumina gel add mixture I and obtain mixture II by ammoniacal liquor adjust ph to 8, mixture II is placed in boiling water bath heating to be concentrated into solid content 55 % by weight and to obtain slurry, slurry is obtained catalyst precursor in 20 hours at 85 DEG C with the heated air drying that relative humidity is 90%, by catalyst precursor at 550 DEG C of roastings, 9 hours obtained catalyst, it consists of: 75%Fe
100mo
25cu
2.5zn
10k
2.5te
0.5o
x+ 25%Si
1al
1o
3.5.Catalyst crushing and screening 20-40 order particle is stand-by.
[embodiment 14]
Get 110.8 grams of ferric nitrates, 0.03 gram of potassium nitrate, 0.76 gram of copper nitrate and 5.65 grams of zinc nitrates are dissolved in 100 ml waters and are made into certain density solution I, by 0.34 gram of ammonium selenate, 24.6 grams of chromic nitrates and 55.9 grams of ammonium heptamolybdates are dissolved in 100 ml waters and obtain solution II, solution II is added in solution I and obtains mixture I, the Alumina gel being 25% by 80 grams of quality of alumina content adds mixture I and obtains mixture II by ammoniacal liquor adjust ph to 8, mixture II is placed in boiling water bath heating to be concentrated into solid content 55 % by weight and to obtain slurry, slurry is obtained catalyst precursor in 8 hours at 90 DEG C with the heated air drying that relative humidity is 90%, by catalyst precursor at 700 DEG C of roastings, 7 hours obtained catalyst, it consists of: 80%Fe
100mo
100cr
22.5cu
1zn
6k
0.1se
0.6o
x+ 20%Al
2o
3.Catalyst crushing and screening 20-40 order particle is stand-by.
[embodiment 15]
Get 229.6 grams of ferric nitrates, 2.32 gram potassium nitrate, 37.1 grams of zinc nitrates and 4.6 grams of copper nitrates are dissolved in 100 ml waters and are made into certain density solution I, 1.34 grams of ammonium tellurates and 13.6 grams of chromic nitrates are dissolved in 100 ml waters and obtain solution II, solution II is added in solution I and obtains mixture I, the Alumina gel being 25% by 120 grams of quality of alumina content adds mixture I and obtains mixture II by ammoniacal liquor adjust ph to 8, mixture II is placed in boiling water bath heating to be concentrated into solid content 55 % by weight and to obtain slurry, slurry is obtained catalyst precursor in 30 hours at 70 DEG C with the heated air drying that relative humidity is 90%, by catalyst precursor at 650 DEG C of roastings, 12 hours obtained catalyst, it consists of: 70%Fe
100cr
6cu
2.9zn
19k
3.5te
0.9o
x+ 30%Al
2o
3.Catalyst crushing and screening 20-40 order particle is stand-by.
[embodiment 16]
Get 127.2 grams of ferric nitrates, 0.73 gram of potassium nitrate and 13.2 grams of copper nitrates are dissolved in 100 ml waters and are made into certain density solution I, 0.26 gram of ammonium selenate and 32.1 grams of ammonium heptamolybdates are dissolved in 100 ml waters and obtain solution II, solution II is added in solution I and obtains mixture I, the Ludox being 40% by 100 grams of siliconoxide mass content adds mixture I and obtains mixture II by ammoniacal liquor adjust ph to 8, mixture II is placed in boiling water bath heating to be concentrated into solid content 55 % by weight and to obtain slurry, slurry is obtained catalyst precursor in 20 hours at 75 DEG C with the heated air drying that relative humidity is 90%, by catalyst precursor at 800 DEG C of roastings, 6 hours obtained catalyst, it consists of: 60%Fe
100mo
50cu
15k
2se
0.4o
x+ 40%SiO
2.Catalyst crushing and screening 20-40 order particle is stand-by.
[embodiment 17]
Get 69.1 grams of ferric nitrates, 1 gram of potassium nitrate and 76.46 grams of zinc nitrates are dissolved in 100 ml waters and are made into certain density solution I, by 0.18 gram of ammonium tellurate, 2.39 gram chromic nitrate, 0.07 gram of ammonium selenate and 1.39 grams of ammonium heptamolybdates are dissolved in 100 ml waters and obtain solution II, solution II is added in solution I and obtains mixture I, by 155.9 grams of siliconoxide mass content be 40% Ludox and 70.6 grams of quality of alumina content be 25% Alumina gel add mixture I and obtain mixture II by ammoniacal liquor adjust ph to 8, mixture II is placed in boiling water bath heating to be concentrated into solid content 55 % by weight and to obtain slurry, slurry is obtained catalyst precursor in 32 hours at 70 DEG C with the heated air drying that relative humidity is 90%, by catalyst precursor at 500 DEG C of roastings, 11 hours obtained catalyst, it consists of: 20%Fe
100cr
3.5mo
4zn
11k
5se
0.2te
0.4o
x+ 80%Si
3al
1o
7.5.Catalyst crushing and screening 20-40 order particle is stand-by.
[comparative example 1]
Get 66.6 grams of ferric nitrates, 0.38 gram of potassium nitrate and 6.9 grams of copper nitrates are dissolved in 100 ml waters and are made into certain density solution I, by 0.14 gram of ammonium selenate, 98.8 grams of chromic nitrates and 16.8 grams of ammonium heptamolybdates are dissolved in 100 ml waters and obtain solution II, solution II is added in solution I and obtains mixture I, the Ludox being 40% by 100 grams of siliconoxide mass content adds mixture I and obtains mixture II by ammoniacal liquor adjust ph to 8, mixture II is placed in boiling water bath heating to be concentrated into solid content 55 % by weight and to obtain slurry, slurry is obtained catalyst precursor in 20 hours at 75 DEG C with the heated air drying that relative humidity is 90%, by catalyst precursor at 800 DEG C of roastings, 6 hours obtained catalyst, it consists of: 60%Fe
100mo
50cr
150cu
15k
2se
0.4o
x+ 40%SiO
2.Catalyst crushing and screening 20-40 order particle is stand-by.
Catalyst composition and preparation condition in table 1, reaction condition with the results are shown in Table 2.
Table 1
Table 2
| Embodiment | Reaction temperature/DEG C | Reaction velocity/h -1 | Reaction pressure/MPa | CO conversion ratio/% | C 2-C 4Olefine selective/wt% |
| Embodiment 1 | 240 | 2000 | 1.5 | 93.4 | 57.4 |
| Embodiment 2 | 270 | 3500 | 2.5 | 92.7 | 63.9 |
| Embodiment 3 | 280 | 4000 | 2.1 | 93.5 | 60.8 |
| Embodiment 4 | 280 | 4000 | 2.1 | 94.5 | 60.1 |
| Embodiment 5 | 280 | 4000 | 2.1 | 90.1 | 57.3 |
| Embodiment 6 | 280 | 4000 | 2.1 | 93.1 | 66.5 |
| Embodiment 7 | 280 | 4000 | 2.1 | 94.2 | 65.9 |
| Embodiment 8 | 280 | 4000 | 2.1 | 93.7 | 67.4 |
| Embodiment 9 | 280 | 4000 | 2.1 | 95.1 | 59.9 |
| Embodiment 10 | 280 | 4000 | 2.1 | 94.3 | 60.4 |
| Embodiment 11 | 220 | 2300 | 0.8 | 86.1 | 58.1 |
| Embodiment 12 | 260 | 3700 | 2.0 | 88.3 | 67.6 |
| Embodiment 13 | 225 | 1500 | 0.6 | 87.6 | 65.3 |
| Embodiment 14 | 245 | 1800 | 0.5 | 94.5 | 60.5 |
| Embodiment 15 | 255 | 2700 | 1.0 | 93.9 | 61.8 |
| Embodiment 16 | 230 | 3000 | 1.2 | 87.2 | 56.4 |
| Embodiment 17 | 250 | 1300 | 1.8 | 98.8 | 59.2 |
| Comparative example 1 | 270 | 1000 | 1.3 | 50 | 35 |
Claims (10)
1. a preparation of low carbon olefines by synthetic gas catalyst, in catalyst weight percent, comprises following component:
The active component of (1) 20 ~ 80%;
The carrier of (2) 20 ~ 80%, carrier is selected from SiO
2or Al
2o
3in at least one;
Described active component can by following general formula with atomic ratio measuring: Fe
100a
ab
bk
co
x
Wherein A is at least one be selected from Cu or Zn;
B is at least one be selected from Cr or Mo;
The span of a is: 5 ~ 50;
The span of b is: 5-150;
The span of c is: 0.1 ~ 5;
X is for meeting the oxygen atom sum needed for other element valence.
2. preparation of low carbon olefines by synthetic gas catalyst according to claim 1, it is characterized in that catalyst is also at least one be selected from Se and Te containing component D, D, the atomic ratio of D and Fe is the span of d:100, d is 0.2-1.
3. preparation of low carbon olefines by synthetic gas catalyst according to claim 1, is characterized in that the span of a is 10 ~ 40.
4. preparation of low carbon olefines by synthetic gas catalyst according to claim 1, is characterized in that the span of b is: 20 ~ 120.
5. preparation of low carbon olefines by synthetic gas catalyst according to claim 1, is characterized in that the span of c is: 0.5 ~ 3.
6. preparation of low carbon olefines by synthetic gas catalyst according to claim 2, is characterized in that the span of d is 0.5-0.8.
7. the preparation method of preparation of low carbon olefines by synthetic gas catalyst described in any one of claim 1 ~ 6, comprises the following steps successively:
(1) soluble-salt containing component Fe, A and K is dissolved in deionized water wiring solution-forming
;
(2) soluble-salt containing B component or D is dissolved in deionized water wiring solution-forming
;
(3) by solution
add solution
middle formation mixture
;
(4) powder or colloidal sol that contain carrier are added mixture
, obtained mixture
;
(5) mixture is regulated with alkali
pH value to 8 ~ 10, the concentrated obtained slurry of heating;
(6) slurry drying obtains catalyst precursor;
(7) catalyst precursor obtains catalyst through roasting.
8. the preparation method of preparation of low carbon olefines by synthetic gas catalyst according to claim 7, it is characterized in that step (5) concentrated after the slurry solid content of gained be 60 ~ 80 % by weight.
9. the preparation method of preparation of low carbon olefines by synthetic gas catalyst according to claim 7, step (6) baking temperature is 70 ~ 90 DEG C, and drying time is 5 ~ 40 hours; Step (7) sintering temperature is 500 ~ 800 DEG C, and roasting time is 2 ~ 12 hours.
10. catalyst described in any one of claims 1 ~ 6 is for the synthesis of gas reaction for preparing light olefins, is 220 ~ 280 DEG C in reaction temperature, and reaction pressure is 0.5 ~ 2.5MPa, volume space velocity 1000-4000h
-1condition under, synthesis gas and described catalyst exposure react and generate low-carbon alkene.
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