CN106607049B

CN106607049B - Catalyst of preparation of low carbon olefines by synthetic gas and preparation method thereof

Info

Publication number: CN106607049B
Application number: CN201510685593.4A
Authority: CN
Inventors: 庞颖聪; 陶跃武; 宋卫林; 李剑锋
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2015-10-21
Filing date: 2015-10-21
Publication date: 2019-04-12
Anticipated expiration: 2035-10-21
Also published as: CN106607049A

Abstract

The present invention relates to catalyst of a kind of preparation of low carbon olefines by synthetic gas and preparation method thereof, it mainly solves in the prior art since Fischer-Tropsch synthesis is strong exothermal reaction, when using fixed bed, cooling is difficult in reactor, easy temperature runaway, the problem for making catalyst be easy to inactivate and low-carbon alkene weight selectivities are low.The catalytic component that the present invention uses contains with atomic ratio measuring, the following composition of chemical formula: Fe₁₀₀MnaB_bC_cO_x, B is selected from least one of Ga or In；C is selected from the technical solution of at least one of Rh or Ir, preferably solves the above problem, the industrial production for one-step method from syngas producing light olefins.

Description

Catalyst of preparation of low carbon olefines by synthetic gas and preparation method thereof

Technical field

The catalyst and preparation method thereof that the present invention relates to a kind of for synthesis gas low-carbon alkene

Background technique

Fischer-Tropsch (Fascher-Tropsch) synthesis is that (main component is CO and H using synthesis gas₂) in the effect of catalyst The process of lower synthesis hydrocarbon, is an important channel of coal and natural gas indirect liquefaction.This method is nineteen twenty-three by Germany scientist Frans Fischer and Hans Tropsch invention, i.e. heterogeneous catalysis hydrogenation occurs on metallic catalyst for CO, raw At the process of the mixture based on linear paraffin and alkene.

Germany has just carried out the research and development to F- T synthesis in the twenties in last century, and realizes industry in 1936 Change, is closed after World War II because can not economically be competed with petroleum industry；South Africa possesses coal resources abundant, but petroleum resources Plaque is weary, and is limited for a long time by international community's economy and political sanction, forces it to develop coal-to-oil industry technology, and in 1955 Having built up First production capacity is 25~400,000 tons of product/year coal base F-T synthetic oil factories (Sasol-1).1973 and World oil crisis twice in 1979 causes world's crude oil price to fall and swings fluctuating, big rise and big fall, is based on Strategic Technology deposit The considerations of, F-T synthetic technology arouses the interest of industrialized country again.

1980 and nineteen eighty-two, South Africa Sasol company builds up in succession again and Liang Zuomeiji synthetic oil factory of having gone into operation.But 1986 Plummeting for year World oil price, has postponed F-T synthetic technology in the heavy industrialization process of other countries.Twentieth century 90 Since age, petroleum resources shortage and in poor quality increasingly, while coal and natural gas proved reserves are but continuously increased, fischer-tropsch technologies It attracts extensive attention again, Fiscber-Tropscb synthesis technology has also obtained significant progress.

Currently used fischer-tropsch catalysts, from active component for be divided into two major classes: ferrum-based catalyst and cobalt-based catalyst Agent；And common synthesis technology is divided into two major classes if classifying from synthesis condition angle: high temperature fischer-tropsch synthesis technology and low temperature Fischer-tropsch synthesis process；Synthesis technology is divided into three categories if classifying from used reactor difference: fixed bed F- T synthesis Technique, fluidized bed fischer-tropsch synthesis process (have the recirculating fluidized bed of early stage and developed on the basis of recirculating fluidized bed later It is fixed fluidized bed) and syrup state bed Fischer Tropsch synthesis technology.Fixed bed therein and slurry bed system are generally used for Low Temperature Fischer Tropsch work Skill is chiefly used in the production of mink cell focus and wax, and fluidized bed is then more suitable for the high temperature fischer-tropsch work of the production more hydro carbons of lightweight Skill.

It in recent years, with the rapid development of our country's economy, is growing day by day to the demand of oil product.The spy of China's energy Point is that rich coal lacks gas oil starvation, and environmental pollution caused by coal directly burns also is taken seriously increasingly.Exploitation is passed through by coal/natural gas Synthesis gas is converted into the process of oil product, not only can reduce to external dependence on the energy, and draws for solving fire coal The problem of environmental pollution risen has great importance.

It is to be suitable for cryogenic high pressure paste state bed reactor that the fischer-tropsch catalysts of document and patent report are more in recent years Produce high-carbon long chain hydrocarbons, it is general it is mostly is precipitated iron catalyst or immersion-type Co catalysts.If Rentech company, the U.S. is special A kind of F- T synthesis precipitated iron catalysis suitable for paste state bed reactor is just reported in sharp USP5504118 and CN1113905A The preparation method of agent.The characteristics of F- T synthesis of light hydrocarbon is general mostly to carry out in a fluidized bed reactor, the technique is reaction temperature Degree is higher, and conversion ratio is higher, and there is no the difficulties of solid-liquor separation.Currently reported is applied to the more of fluidized bed F- T synthesis For molten iron type catalyst, occasionally there is some type of precipitated iron catalyst.One kind is referred to if in patent CN1704161A to be used for The preparation of the molten iron type catalyst of F- T synthesis is referred to a kind of precipitated iron for fluidized bed in patent CN1695804A and is catalyzed Agent.

Preparing low-carbon olefin has direct method and indirect method, is specific under so-called direct method i.e. specified conditions High temperature fischer-tropsch synthesis under catalyst.Although at present have it is some by fixed bed applications in high temperature fischer-tropsch be used for low-carbon alkene production It attempts, such as Rule of Germany, the DaLian, China Chemistry and Physics Institute, but since Fischer-Tropsch synthesis is strong exothermal reaction, uses fixed bed When, cooling is difficult in reactor, Yi Feiwen, and catalyst is made to be easy inactivation, these trials terminate in laboratory stage.Fluidized bed can To overcome these problems existing for fixed bed well, but prepared by the catalyst or the precipitation method that are either prepared using molten iron method Fluidized Multicomponent Metallic Oxides Catalysts wide, the low disadvantage of selectivity of light olefin that all there is product distribution at present.

Summary of the invention

The first technical problem to be solved by the present invention is existing in the prior art since Fischer-Tropsch synthesis is to put by force Thermal response, when using fixed bed, reaction cooling is difficult, Yi Feiwen, and catalyst is made to be easy inactivation and the selection of low-carbon alkene weight Property low problem, a kind of catalyst of new direct producing light olefins of one step of synthesis gas is provided.The catalyst is closed for fluidized bed When at low-carbon alkene, have reaction cooling fast, is not easy temperature runaway and the high advantage of low-carbon alkene weight selectivities.

The technical solution adopted by the present invention one is as follows to solve above-mentioned technical problem: a kind of preparation of low carbon olefines by synthetic gas is urged Agent.The catalytic component contains with atomic ratio measuring, chemical formula Fe₁₀₀Mn_aB_bC_cO_xComposition: B be selected from Ga or In at least One kind, C are selected from least one of Rh or Ir, and the value range that the value range of a is 25.0~250.0, b is 0.5~20.0, The value range of c is that 0.1~10.0, x is to meet the sum of oxygen atom needed for each element chemical valence in catalyst.

Catalyst formulation is optimized for active component also and includes element D in above-mentioned technical proposal, and D is that alkali metal is a kind of, D with The ratio of Fe is Fe:D=100:d with atomic ratio measuring, and the value range of d is 0.05~5.0.

Carrier dosage preferred scope is 15~65%, a of catalyst weight by weight percentage in above-mentioned technical proposal Value preferred scope be 50~200.0, b value preferred scope be 1.0~15.0, c value preferred scope be 0.5~ 8.0, d value preferred scope is 0.1~4.5.

The technical solution adopted by the present invention two is as follows to solve above-mentioned technical problem: the catalyst of preparation of low carbon olefines by synthetic gas Preparation method, comprise the following steps that:

(1) by Dissolvable Fe salt with celite is soluble in water that solution is made；Then be obtained by filtration after alkaline precipitating agent cocurrent it is mixed Close sediment I；

(2) solution II is made by soluble M n salt and B salt are soluble in water；

(3) solution II is mixed into peptization with mixed sediment I and obtains slurry III；

(4) compound solution of D is added in slurry III, is mixed with beating, while acid-base modifier is added and adjusts slurry PH value be 1~5 to obtain slurry IV, the solid content of slurry IV is 15~45 weight %；

(5) slurry IV is sent into spray dryer spray shaping, it is then small in 400~750 DEG C of roasting temperatures 0.15~6 When, obtain microspheroidal Fe base catalyst.

Inlet temperature range is 200~380 DEG C in the spray shaping condition of catalyst described in above-mentioned technical proposal, outlet The range of temperature is 100~230 DEG C.

The preferred scope of catalyst maturing temperature described in above-mentioned technical proposal is 450~700 DEG C, the catalyst roasting The preferred scope of time is 0.5~5h.

Catalyst is can be improved into due to the addition of noble metal Rh or Ir in the catalyst according to said method obtained plus hydrogen Can, so that the conversion ratio of catalyst improves, while noble metal and Mn synergistic effect substantially increase the property of the CO absorption of catalyst Can, so that the selectivity of alkene will be significantly larger than the selectivity of alkane.Special preparation method and component ratio not needing Add additional inert component do carrier can improve catalyst active component dispersion degree and catalyst intensity, together When can it is higher improve catalyst efficiency, it can under higher air speed use catalyst；Good dispersion degree simultaneously Active component can be reduced because of reunion caused by area carbon, allow the catalyst keep for a long time high conversion ratio and The selectivity of high low-carbon alkene is highly suitable for the industrial application of the direct synthesizing low-carbon alkene of synthesis gas.

Above-mentioned catalyst is reacted for F- T synthesis low-carbon alkene, first uses H₂The synthesis gas for being 0.25 with CO molar ratio exists 1.5MPa, 450 DEG C, air speed is 1000 hours^-1Lower reductase 12 4 hours, then using synthesis gas as unstripped gas, H₂It is with CO molar ratio 3, it is 1.5MPa in reaction pressure, reaction temperature is 350 DEG C, and reaction volume air speed is 15000 hours^-1Under conditions of, it is fluidizing Unstripped gas is contacted with catalyst in bed reactor, and achieve preferable technical effect: the conversion ratio of CO is up to 97%, Dan Shi C₂ ⁼- C₄ ⁼The weight selectivities of (ethylene, propylene and butylene) component are up to 73%.

The present invention will be further described below by way of examples.

Specific embodiment

[embodiment 1]

1) rhodium chloride of the Fe(NO3)39H2O and 0.314g that take 606.03g wiring solution-forming soluble in water, then this is molten It is centrifugated after liquid and the concentrated ammonia liquor cocurrent of 25 weight % of 400g, is washed with deionized and obtains fresh hydroxide afterwards three times The mixed precipitation I of iron and rhodium oxide；

2) manganese nitrate of 50 weight % of 134.5g and nine nitric hydrate gallium of 3.13g are dissolved in the water and solution II is made；

3) it is mixed with beating solution II and mixed sediment I to obtain colloidal slurry III；

4) potassium hydroxide of 0.042g is dissolved in water to be then added in slurry III, is mixed with beating, adjust slurry with ammonium hydroxide PH value be 5, obtain sol form and be uniformly dispersed and place the uniform sizing material IV (solid content 45%) that will not be layered for a long time；

5) by IV spray drying forming of slurry, spraying machine inlet temperature is 380 DEG C, 230 DEG C of outlet temperature, is then roasted It burns, 750 DEG C of maturing temperature, calcining time 6h；

The microspheric fluidized bed iron that can be used for the direct producing light olefins of one step of synthesis gas is obtained by above-mentioned steps Manganese series catalyzer, group, which is made, to be become (except special identifier all components ratio is atomic ratio):

Fe₁₀₀Mn_25.0Ga_0.5Rh_0.1K_0.05O_x

[embodiment 2]:

1) iridous chloride of the Fe(NO3)39H2O and 44.79g that take 606.03g wiring solution-forming soluble in water, then this is molten It is centrifugated after liquid and the concentrated ammonia liquor cocurrent of 25 weight % of 400g, is washed with deionized and obtains fresh hydroxide afterwards three times The mixed precipitation I of iron and yttrium oxide；

2) manganese nitrate of 50 weight % of 1345g and five nitric hydrate indium of 117.3g are dissolved in the water and solution II is made；

4) 4.20g potassium hydroxide is dissolved in water to be then added in slurry III, is mixed with beating, adjust slurry with dust technology PH value is 1, obtains sol form and is uniformly dispersed and places the uniform sizing material IV (solid content 15%) that will not be layered for a long time；

5) by IV spray drying forming of slurry, spraying machine inlet temperature is 200 DEG C, 100 DEG C of outlet temperature, is then roasted It burns, 450 DEG C of maturing temperature, calcining time 0.15h；

The microspheric fluidized bed iron that can be used for the direct producing light olefins of one step of synthesis gas is obtained by above-mentioned steps Mn catalyst, group, which is made, to be become (except special identifier all components ratio is atomic ratio):

Fe₁₀₀Mn_250.0In_20.0Ir_10.0K_5.0O_x

[embodiment 3]:

1) rhodium chloride of 367.43g ironic citrate and 1.57g wiring solution-forming soluble in water are taken, then the solution and 400g It is centrifugated after the concentrated ammonia liquor cocurrent of 25 weight %, is washed with deionized and obtains fresh iron hydroxide and rhodium oxide afterwards three times Mixed precipitation I；

2) manganese nitrate of 50 weight % of 269.0g and nine nitric hydrate gallium of 125.2g are dissolved in the water and solution II is made；

4) 1.05g sodium hydroxide is dissolved in water to be then added in slurry III, is mixed with beating, while adjusted and being starched with weak aqua ammonia The pH value of material is 3, obtains sol form and is uniformly dispersed and places the uniform sizing material IV (solid content 35%) that will not be layered for a long time；

5) by IV spray drying forming of slurry, spraying machine inlet temperature is 230 DEG C, 140 DEG C of outlet temperature, then into Row roasting, 400 DEG C of maturing temperature, calcining time 5h；

The microspheric fluidized bed for the direct producing light olefins of one step of synthesis gas is obtained by above-mentioned steps to be urged with ferrimanganic Agent, group, which is made, to be become (except special identifier all components ratio is atomic ratio):

Fe₁₀₀Mn_50.0Ga_20.0Rh_0.5Na_1.75O_x

[embodiment 4]:

1) rhodium chloride of the Fe(NO3)39H2O and 25.12g that take 606.03g wiring solution-forming soluble in water, then this is molten It is centrifugated after liquid and the concentrated ammonia liquor cocurrent of 25 weight % of 400g, is washed with deionized and obtains fresh hydroxide afterwards three times The mixed precipitation I of iron and rhodium oxide；

2) manganese nitrate of 1076g50 weight % and five nitric hydrate indium of 58.7g are dissolved in the water and solution II is made；

4) 0.54g lithium hydroxide is dissolved in water to be then added in slurry III, is mixed with beating, adjust slurry with weak aqua ammonia PH value is 2.5, obtains sol form and is uniformly dispersed and places the uniform sizing material IV (solid content 30%) that will not be layered for a long time；

5) by IV spray drying forming of slurry, spraying machine inlet temperature is 280 DEG C, 150 DEG C of outlet temperature, is then roasted It burns, 700 DEG C of maturing temperature, calcining time 0.5h；

Fe₁₀₀Mn_200.0In_10.0Rh_8.0Li_1.5O_x

[embodiment 5]:

1) iridous chloride of the Fe(NO3)39H2O and 2.24g that take 606.03g wiring solution-forming soluble in water, the then solution It is centrifugated with after the concentrated ammonia liquor cocurrent of 25 weight % of 400g, is washed with deionized and obtains fresh iron hydroxide afterwards three times With the mixed precipitation I of yttrium oxide；

2) manganese nitrate of 50 weight % of 538.0g and nine nitric hydrate gallium of 62.6g and five nitric hydrate indium of 58.7g are dissolved Solution II is made in Yu Shuizhong；

4) 3.31g rubidium nitrate is dissolved in water to be added in slurry III, is mixed with beating, the pH of slurry is then adjusted with dust technology Value is 3.5, obtains sol form and is uniformly dispersed and places the uniform sizing material IV (solid content 25%) that will not be layered for a long time；

5) by the slurry spray drying forming, spraying machine inlet temperature is 330 DEG C, 200 DEG C of outlet temperature, is then roasted It burns, 450 DEG C of maturing temperature, calcining time 3.4h；

Fe₁₀₀Mn_100.0Ga_10.0In_10.0Ir_0.5Rb_0.5O_x

[embodiment 6]:

1) it takes the rhodium chloride of the Fe(NO3)39H2O of 606.03g and the iridous chloride of 2.24g and 0.63g to be dissolved in water to match It at solution, is then centrifugated after the solution and the concentrated ammonia liquor cocurrent of 25 weight % of 400g, is washed with deionized and obtains afterwards three times To the mixed precipitation I of fresh iron hydroxide and yttrium oxide and rhodium oxide；

4) 1.59g strontium nitrate is dissolved in water to be then added in slurry III, is mixed with beating, while adjusting slurry with weak aqua ammonia PH value be 4.5, obtain sol form and be uniformly dispersed and place the uniform sizing material IV (solid content 20%) that will not be layered for a long time；

5) by IV spray drying forming of slurry, spraying machine inlet temperature is 360 DEG C, 220 DEG C of outlet temperature, is then roasted It burns, 550 DEG C of maturing temperature, calcining time 1.4h；

Fe₁₀₀Mn_200.0In_10.0Rh_0.2Ir_0.5Sr_0.5O_x

[embodiment 7]:

4) 4.5g cesium hydroxide is dissolved in water to be then added in slurry III, is mixed with beating, adjust slurry with dust technology PH value is 3.5, obtains sol form and is uniformly dispersed and places the uniform sizing material IV (solid content 25%) that will not be layered for a long time；

5) by IV spray drying forming of slurry, spraying machine inlet temperature is 260 DEG C, 130 DEG C of outlet temperature, is then roasted It burns, 550 DEG C of maturing temperature, calcining time 4h；

Fe₁₀₀Mn_200.0In_10.0Rh_0.2Ir_0.5Cs_2.0O_x

[embodiment 8]:

2) manganese nitrate of 1076g50 weight % and five nitric hydrate indium of 58.7g and nine nitric hydrate gallium of 62.6g are dissolved Solution II is made in Yu Shuizhong；

4) it takes 1.68g potassium hydroxide to be dissolved in water to be then added in slurry III, be mixed with beating, adjust slurry with dust technology PH value is 1.5, obtains sol form and is uniformly dispersed and places the uniform sizing material IV (solid content 20%) that will not be layered for a long time；

5) by IV spray drying forming of slurry, spraying machine inlet temperature is 290 DEG C, 180 DEG C of outlet temperature, is then roasted It burns, 650 DEG C of maturing temperature, calcining time 3h；

Fe₁₀₀Mn_200.0In_10.0Ga_10.0Rh_0.2Ir_0.5K₂O_x

[embodiment 9]:

4) by the SiO of 1530g weight content 40%₂Colloidal sol is added in slurry III, and the hydroxide of 0.042g is then added Potassium is mixed with beating, and is 4.7 with the pH value that ammonium hydroxide adjusts slurry, is obtained sol form and is uniformly dispersed and places for a long time and will not be layered Uniform sizing material IV (solid content 20%)；

5) by IV spray drying forming of slurry, spraying machine inlet temperature is 350 DEG C, 215 DEG C of outlet temperature, is then roasted It burns, 650 DEG C of maturing temperature, calcining time 5.2h；

35 weight %Fe₁₀₀Cu_0.5Mg_20.0Rh_0.1K_0.05O_x+ 65 weight %SiO₂

[embodiment 10]

4) by the SiO of 1530g weight content 40%₂Colloidal sol is added in slurry III, and 1.68g potassium hydroxide is then added, It is mixed with beating, is 1.5 with the pH value that dust technology adjusts slurry, obtain sol form and be uniformly dispersed and place for a long time and will not be layered Uniform sizing material IV (solid content 20%)；

Fe₁₀₀Mn_200.0In_10.0Ga_10.0Rh_0.2Ir_0.5K₂O_x+ 65 weight %SiO₂

[comparative example 1]

2) manganese nitrate of 50 weight % of 134.5g is dissolved in the water and solution II is made；

Fe₁₀₀Mn_25.0Rh_0.1K_0.05O_x

[comparative example 2]

1) Fe(NO3)39H2O of 606.03g wiring solution-forming soluble in water is taken, then the solution is with 25 weight %'s of 400g It is centrifugated after concentrated ammonia liquor cocurrent, the mixed precipitation for obtaining fresh iron hydroxide and rhodium oxide afterwards three times is washed with deionized Ⅰ；

Fe₁₀₀Mn_25.0Ga_0.5K_0.05O_x

[comparative example 3]:

2) nine nitric hydrate gallium of 13.13g is dissolved in the water and solution II is made；

3) it is mixed with beating solution II and mixed sediment I to obtain slurry III；

4) potassium hydroxide of 0.042g is dissolved in water to be then added in slurry III, is mixed with beating, adjusted and starched with dust technology The pH value of material is 5, obtains sol form and is uniformly dispersed and places the uniform sizing material IV (solid content 45%) that will not be layered for a long time；

The microspheric fluidized bed iron that can be used for the direct producing light olefins of one step of synthesis gas is obtained by above-mentioned steps Series catalysts, group, which is made, to be become (except special identifier all components ratio is atomic ratio):

Fe₁₀₀Ga_0.5Rh_0.1K_0.05O_x

[comparative example 4]

Fixed bed catalyst is prepared using method described in CN 1395993A, is formulated identical with embodiment 3

Obtained above-mentioned catalyst carries out Fischer-Tropsch synthesis in addition to comparative example 3 under following reaction conditions, as a result It is listed in table.

Reducing condition are as follows:

450 DEG C of temperature

Pressure 1.5MPa

50 grams of loaded catalyst

Catalyst loading (reaction volume air speed) 1000 hours^-1

Also Primordial Qi H₂/ CO=0.25/1

Recovery time 24 hours

Reaction condition are as follows:

38 millimeters of fluidized-bed reactors of φ

350 DEG C of reaction temperature

Reaction pressure 1.5MPa

50 grams of loaded catalyst

Catalyst loading (reaction volume air speed) 15000 hours^-1

Raw material proportioning (mole) H₂/ CO=3/1

By comparative example 3 by evaluation analysis result is listed in table in fixed bed described in patent CN 1395993A

^#It is reacted to data when 2000h

* the data of former patent are selected from.

Claims

1. a kind of catalyst for preparation of low carbon olefines by synthetic gas, catalyst contains with atomic ratio measuring, the following combination of chemical formula Object: Fe₁₀₀Mn_aB_bC_cO_x

B is selected from at least one of Ga or In；

C is selected from least one of Rh or Ir；

The value range of a is 25~250.0；

The value range of b is 0.5~20.0；

The value range of c is 0.1~10.0；

X is to meet the sum of oxygen atom needed for each element chemical valence in catalyst；

Its active component also includes element D, and D is that alkali metal is a kind of, and the ratio of D and Fe are Fe:D=100:d with atomic ratio measuring, d's Value range is 0.05 ~ 5.0.

2. the catalyst according to claim 1 for preparation of low carbon olefines by synthetic gas, it is characterised in that the value range of a is 50~200.0.

3. the catalyst according to claim 1 for preparation of low carbon olefines by synthetic gas, it is characterised in that the value range of b is 1.0~15.0.

4. the catalyst according to claim 1 for preparation of low carbon olefines by synthetic gas, it is characterised in that the value range of c is 0.5~8.0.

5. the catalyst according to claim 1 for preparation of low carbon olefines by synthetic gas, it is characterised in that the value range of d is 0.1~4.5.

6. the catalyst described in claim 1 for preparation of low carbon olefines by synthetic gas, comprises the following steps that:

(1) by Dissolvable Fe salt with celite is soluble in water that solution is made；Then be obtained by filtration after alkaline precipitating agent cocurrent mix it is heavy Starch I；

(2) solution II is made by soluble M n salt and B salt are soluble in water；

(4) compound solution of D is added in slurry III, is mixed with beating, while the pH that acid-base modifier adjusts slurry is added Value obtains slurry IV for 1 ~ 5, and the solid content of slurry IV is 15 ~ 45 weight %；

(5) by slurry IV be sent into spray dryer spray shaping, then 400 ~ 750 DEG C roasting temperature 0.15 ~ 6 hour, Obtain micro-spherical catalyst particle.

7. the catalyst according to claim 6 for preparation of low carbon olefines by synthetic gas, it is characterised in that catalyst is sprayed Condition of molding is 200 ~ 380 DEG C of inlet temperature, 100 ~ 230 DEG C of outlet temperature.

8. the catalyst according to claim 7 for preparation of low carbon olefines by synthetic gas, it is characterised in that maturing temperature 450 ~ 700 DEG C, calcining time is 0.5 ~ 5 hour.