CN106607037A - GTO catalyst used for fluidized bed and preparation method of GTO catalyst - Google Patents
GTO catalyst used for fluidized bed and preparation method of GTO catalyst Download PDFInfo
- Publication number
- CN106607037A CN106607037A CN201510683782.8A CN201510683782A CN106607037A CN 106607037 A CN106607037 A CN 106607037A CN 201510683782 A CN201510683782 A CN 201510683782A CN 106607037 A CN106607037 A CN 106607037A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- gto
- fluid bed
- slurry
- weight
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a GTO (direct preparation of low carbon olefin from synthetic gas) catalyst used for a fluidized bed and a preparation method of the GTO catalyst. The problem that in the prior art, since the Fischer-Tropsch synthesis is a strong exothermic reaction, when a fluidized bed is used, heat in a reactor is hard to dissipate, so that the temperature is easy to rise, the catalyst is prone to be inactivated, and the weight selectivity of low-carbon olefin is low is mainly solved. The GTO catalyst comprises, by weight part, a) 10-70 parts of a carrier selected from at least one of a Zr or Ti oxide, and b) 30-90 parts of an active component including, based on an atomic ratio, the following composition having a chemical formula of Fe<100>A<a>B<b>C<c>O<x>, wherein A is selected from one of Zn or Cd, B is elected from one of Ga or In, and C is one of alkaline-earth metals. According to the technical scheme, the problem is well solved. The GTO catalyst can be used for industrial production of low-carbon olefin through the Fischer-Tropsch synthesis.
Description
Technical field
The present invention relates to a kind of GTO catalyst for fluid bed and preparation method thereof
Background technology
With the fast development of China's economy, it is to grow with each passing day to the demand of petroleum resources and products thereof.The characteristics of China's energy is the few gas oil starvation of rich coal, the deficient stem reality for having become China's energy development with domestic petroleum insufficient supply of petroleum resources, with the development of national economy, contradiction between oil supply and demand will expand trend in persistence, break away from energy resource structure for the dependence of petroleum resources has become extremely urgent problem demanding prompt solution.This just promotes people actively and hardy to go to develop other alternative energy sources, along with directly the burn environmental pollution that causes of coal is also taken seriously increasingly.Exploitation is converted into the process of low-carbon alkene and liquid fuel by coal/natural gas ECDC into gas, can not only be reduced to external dependence on the energy, and is had great importance for the coal-fired problem of environmental pollution for causing is solved.
Fischer-Tropsch (Fascher-Tropsch) synthesis is that (main component is CO and H using synthesis gas2) process of synthesis hydrocarbon in the presence of catalyst, it is an important channel of coal and natural gas indirect liquefaction.The method is to be invented by Germany scientist Frans Fischer and Hans Tropsch nineteen twenty-three, i.e. CO occurs heterogeneous catalysis hydrogenation on metallic catalyst, generates the process of the mixture based on linear paraffin and alkene.Germany has just carried out research and development in the twenties in last century, and realizes industrialization in 1936, closes because economically competing with petroleum industry after World War II；South Africa possesses abundant coal resources, but petroleum resources plaque is weary, and limited by international community's economy and political sanction for a long time, its development coal-to-oil industry technology is forced, and coal base F-T artificial oils factory (Sasol-1) that First production capacity is 25～400,000 tons of product/years has been built up in 1955.The world oil crisis twice of 1973 and 1979, cause world's crude oil price to fall and swing fluctuating, big rise and big fall, and based on the consideration that Strategic Technology is laid in, F-T synthetic technologys arouse the interest of industrialized country again.1980 and nineteen eighty-two, South Africa Sasol companies build up and have gone into operation Liang Zuomeiji artificial oils factory again in succession.But plummeting for World oil price in 1986, has postponed F-T synthetic technologys in other national heavy industrialization processes.Since twentieth century nineties, petroleum resources shortage and in poor quality increasingly, while coal and natural gas proved reserves are but continuously increased, fischer-tropsch technologies cause extensive concern, Fiscber-Tropscb synthesis technology also to obtain significant progress again.Current conventional fischer-tropsch catalysts, from active component for be divided into two big class：Ferrum-based catalyst and cobalt-base catalyst；And common synthesis technique is divided into two big class if classifying from synthesis condition angle：High temperature fischer-tropsch synthesis technique and Low Temperature Fischer Tropsch synthesis technique；Synthesis technique from using reactor difference being divided into three major types if classifying：Fixed bed fischer-tropsch synthesis process, fluid bed fischer-tropsch synthesis process (have early stage recirculating fluidized bed and developed on the basis of recirculating fluidized bed later it is fixed fluidized bed) and syrup state bed Fischer Tropsch synthesis technique.Fixed bed therein is generally used for low temperature fischer-tropsch process with slurry bed system, is used for the production of mink cell focus and wax, and fluid bed is then more suitable for producing the high temperature fischer-tropsch technique of the more hydro carbons of lightweight
What the fischer-tropsch catalysts of document and patent report were more in recent years applies to cryogenic high pressure paste state bed reactor to produce high-carbon long chain hydrocarbons, and general mostly is precipitated iron catalyst, or immersion-type Co catalysts.A kind of preparation method of the F- T synthesis precipitated iron catalyst suitable for paste state bed reactor is reported if Rentech companies of the U.S. are in patent USP5504118 and CN1113905A.The F- T synthesis of light hydrocarbon it is general it is many carry out in a fluidized bed reactor, be that reaction temperature is higher the characteristics of the technique, conversion ratio is higher, the difficulty that there is no solid-liquor separation.The currently reported mostly molten iron type catalyst for being applied to fluid bed F- T synthesis, occasionally has some type of precipitated iron catalyst.A kind of preparation of the molten iron type catalyst for F- T synthesis is referred to if in patent CN1704161A, a kind of precipitated iron catalyst for fluid bed in patent CN1695804A, is referred to.But all there is products distribution width, the low shortcoming of selectivity of light olefin in Fluidized Multicomponent Metallic Oxides Catalysts prepared by the catalyst for either being prepared using molten iron method or the sedimentation method.
Preparing low-carbon olefin has direct method and indirect method, is the high temperature fischer-tropsch synthesis under specific catalyst under so-called direct method i.e. specified conditions.Although there is some that fixed bed applications are used for the trial of low-carbon alkene production in high temperature fischer-tropsch at present, such as Rule of Germany, the DaLian, China Chemistry and Physics Institute, but as Fischer-Tropsch synthesis are strong exothermal reaction, during using fixed bed, in reactor, remove hot difficulty, easy temperature runaway, catalyst is easily inactivated, these trials terminate in laboratory stage, there is presently no and any industrial application in terms of low-carbon alkene is directly prepared about synthesis gas.
The content of the invention
One of the technical problem to be solved is as Fischer-Tropsch synthesis are strong exothermal reaction present in prior art, during using fixed bed, hot difficulty is removed in reaction, easy temperature runaway, make the catalyst easily low problem of inactivation and low-carbon alkene weight selectivities, there is provided a kind of GTO catalyst of new fluid bed, when the catalyst is used for the reaction of F- T synthesis low-carbon alkene, remove hot fast with reaction, be difficult the high advantage of temperature runaway and low-carbon alkene weight selectivities.
To solve above-mentioned technical problem, technical scheme is as follows：A kind of GTO catalyst for fluid bed, catalyst in terms of parts by weight, including following components：
A) 10～70 parts of carriers, carrier are at least one in the oxide of Zr or Ti；
B) 30～90 parts of active components, active component contain with atomic ratio measuring, the following compositionss of chemical formula：
Fe100AaBbCcOx
The one kind of A in Zn or Cd；
The one kind of B in Ga or In；
The one kind of C in alkaline-earth metal；
The span of a is 0.5～200.0；
The span of b is 0.1～10.0；
The span of c is 0.1～10.0；
Oxygen atom sums of the x in meet catalyst needed for each element quantivalence.
Preferably, the catalyst also active component also includes element D, and D is that alkali metal is a kind of, and the ratio of D and Fe is with atomic ratio measuring as Fe：D=100：The span of d, d is 0.05～5.0.
In above-mentioned technical proposal, carrier consumption preferred scope is the 15～65% of catalyst weight by weight percentage, the value preferred scope of a is 0.8～150.0, the value preferred scope of b is 0.1～4.5 for the value preferred scope of 0.15～9.0, d for the value preferred scope of 0.8～45.0, c.
It is as follows to solve two the technical solution used in the present invention of above-mentioned technical problem：For the preparation method of the GTO catalyst of fluid bed, comprise the following steps that：
(1) solution I is made by soluble ferric iron salt soluble in water；
(2) alite is made into solution with belit is soluble in water, then be filtrated to get after precipitating with alkaline precipitating agent cocurrent (saline solution and alkaline precipitating agent being added in same container, the unit interval enters the saline solution of the container and alkaline precipitating agent just can reaction precipitation completely) simultaneously the mixed oxide II of A and B；
(3) solution I is mixed into beating with mixed oxide II and obtains slurry III；
(4) will be selected from ZrO2Or TiO2In at least one colloidal sol and the hydroxide or saline solution of C and D be added in slurry III, mixing beating, while adding the pH value that acid-base modifier adjusts slurry to be 1～5 to obtain slurry IV, IV solid content of slurry is 15～45 weight %；
(5) slurry IV is sent into into spray dryer spray shaping, then in 400～750 DEG C of roasting temperatures 0.15～6 hour, obtains microsphere shaped iron based catalyst.
The spray shaping condition of the catalyst is 200～380 DEG C for the preferred scope of inlet temperature, and the preferred scope of outlet temperature is 100～230 DEG C.
The preferred scope of the catalyst sintering temperature is 450～700 DEG C；
The preferred scope of the catalyst roasting time is 0.5～5h；
The catalyst for according to said method obtaining can greatly improve the hydrogenation activity of catalyst due to the addition of a small amount of Zn or Cd, alkaline-earth metal can then improve chemisorbed performance of the catalyst to CO, the synergism of the two can greatly improve the activity of catalyst, the addition of Ga or In simultaneously can then suppress the further hydrogenation of alkene, prevent the generation of excessive alkane, so that the amount of alkene is far longer than the amount of alkane in product, the active component of the catalyst of special preparation method molding is more disperseed, active surface can be more, and the duct at the same time being formed is more conducive to formation and the desorption of lower carbon number hydrocarbons, cooperative effect between these characteristics and each component causes the catalyst to be very beneficial for the synthesis of low-carbon alkene, detailed evaluation result sees attached list.
Above-mentioned catalyst is reacted for F- T synthesis low-carbon alkene, with synthesis gas as unstripped gas, H2It is 2 with CO mol ratios, is 1.75MPa in reaction pressure, reaction temperature is 300 DEG C, and reaction volume air speed is 10000 hours-1Under conditions of, unstripped gas is contacted with catalyst in a fluidized bed reactor, achieves preferable technique effect：The conversion ratio of CO is up to 93%, C2 =-C4 =The weight selectivities of (ethylene, propylene and butylene) component are up to 70%.
Below by embodiment, the invention will be further elaborated.
Specific embodiment
【Embodiment 1】
Take the Fe(NO3)39H2O wiring solution-forming soluble in water I of 606.03g；2.23g zinc nitrate hexahydrates and nine nitric hydrate galliums of 313.3g are dissolved in the water and make solution, then by the solution and the 6 weight % ammonia spirit parallel-flow precipitations of 700g, the precipitation is filtered, and the Zinc Oxide of fresh clean and the mixed oxide II of gallium oxide after deionized water cyclic washing, are obtained, solution I is mixed into beating with mixed oxide II and obtains slurry III；By the ZrO of 5.31g weight contents 40%2Colloidal sol is added in slurry III with 0.35g four water-calcium nitrates and 0.042g potassium hydroxide, mixing beating, the pH value that slurry is adjusted with ammonia simultaneously is 5, obtain slurry IV (solid content 15%), by the slurry spray drying forming, spraying machine inlet temperature is 380 DEG C, 230 DEG C of outlet temperature, then carry out roasting, 750 DEG C of sintering temperature, roasting time 6h, obtains microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst, and which is made and consists of (except special identifier all components ratio is atomic ratio)：
90 weight %Fe100Zn0.5Ga50Ca0.1K0.05Ox+ 10 weight %ZrO2。
【Embodiment 2】
Take the Fe(NO3)39H2O wiring solution-forming soluble in water I of 606.03g；892.0g zinc nitrate hexahydrates and nine nitric hydrate galliums of 3.13g are dissolved in the water and make solution, then by the solution and the 6 weight % ammonia spirit parallel-flow precipitations of 1860g, the precipitation is filtered, and the Zinc Oxide of fresh clean and the mixed oxide II of gallium oxide after deionized water cyclic washing, are obtained, solution I is mixed into beating with mixed oxide II and obtains slurry III；By the ZrO of 1692g weight contents 40%2Colloidal sol is added in slurry III with 38.4g magnesium nitrate hexahydrates and 4.20g potassium hydroxide, mixing beating, the pH value that slurry is adjusted with dust technology simultaneously is 1, obtain slurry IV (solid content 45%), by the slurry spray drying forming, spraying machine inlet temperature is 200 DEG C, 100 DEG C of outlet temperature, then carry out roasting, 400 DEG C of sintering temperature, roasting time 0.15h, obtains microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst, and which is made and consists of (except special identifier all components ratio is atomic ratio)：
30 weight %Fe100Zn200Ga0.5Mg10K5Ox+ 70 weight %ZrO2。
【Embodiment 3】
Take the Fe(NO3)39H2O wiring solution-forming soluble in water I of 606.03g；Five nitric hydrate indiums of 780.5g zinc nitrate hexahydrates and 4.69g are dissolved in the water and make solution, then by the solution and the 6 weight % ammonia spirit parallel-flow precipitations of 1620g, the precipitation is filtered, and the Zinc Oxide of fresh clean and the mixed oxide II of Indium sesquioxide. after deionized water cyclic washing, are obtained, solution I is mixed into beating with mixed oxide II and obtains slurry III；By the ZrO of 154g weight contents 40%2Colloidal sol is added in slurry III with 28.62g strontium nitrates and 1.05g sodium hydroxide, mixing beating, the pH value that slurry is adjusted with dust technology simultaneously is 2.3, obtain slurry IV (solid content 35%), by the slurry spray drying forming, spraying machine inlet temperature is 300 DEG C, 180 DEG C of outlet temperature, then carry out roasting, 450 DEG C of sintering temperature, roasting time 0.5h, obtains microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst, and which is made and consists of (except special identifier all components ratio is atomic ratio)：
85 weight %Fe100Zn175In0.8Sr9Na1.75Ox+ 15 weight %TiO2。
【Embodiment 4】
Take the Fe(NO3)39H2O wiring solution-forming soluble in water I of 606.03g；Five nitric hydrate indiums of tetra- water cadmium nitrates of 3.70g and 263.81g are dissolved in the water and make solution, then by the solution and the 6 weight % ammonia spirit parallel-flow precipitations of 630g, the precipitation is filtered, and the Aska-Rid. of fresh clean and the mixed oxide II of Indium sesquioxide. after deionized water cyclic washing, are obtained, solution I is mixed into beating with mixed oxide II and obtains slurry III；By the TiO of 1304g weight contents 30%2Colloidal sol is added in slurry III with 0.59g barium nitrates and 0.54g Lithium hydrates, mixing beating, the pH value that slurry is adjusted with dust technology simultaneously is 1.8, obtain slurry IV (solid content 25%), by the slurry spray drying forming, spraying machine inlet temperature is 320 DEG C, 190 DEG C of outlet temperature, then carry out roasting, 700 DEG C of sintering temperature, roasting time 5h, obtains microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst, and which is made and consists of (except special identifier all components ratio is atomic ratio)：
35 weight %Fe100Cd0.8In45Ba0.15Li1.5Ox+ 65 weight %TiO2。
【Embodiment 5】
Take the Fe(NO3)39H2O wiring solution-forming soluble in water I of 606.03g；Five nitric hydrate indiums of tetra- water cadmium nitrates of 3.70g and 263.81g are dissolved in the water and make solution, then by the solution and the 6 weight % ammonia spirit parallel-flow precipitations of 630g, the precipitation is filtered, and the Aska-Rid. of fresh clean and the mixed oxide II of Indium sesquioxide. after deionized water cyclic washing, are obtained, solution I is mixed into beating with mixed oxide II and obtains slurry III；By the TiO of 1304g weight contents 30%2Colloidal sol is added in slurry III with 0.58g magnesium nitrates and 3.31g rubidium nitrates, mixing beating, the pH value that slurry is adjusted with weak ammonia simultaneously is 4.5, obtain slurry IV (solid content 20%), by the slurry spray drying forming, spraying machine inlet temperature is 260 DEG C, 140 DEG C of outlet temperature, then carry out roasting, 500 DEG C of sintering temperature, roasting time 5h, obtains microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst, and which is made and consists of (except special identifier all components ratio is atomic ratio)：
35 weight %Fe100Cd0.8In45Mg0.15Rb0.5Ox+ 65 weight %TiO2。
【Embodiment 6】
Take the Fe(NO3)39H2O wiring solution-forming soluble in water I of 606.03g；89.2g zinc nitrate hexahydrates and nine nitric hydrate galliums of 125.2g are dissolved in the water and make solution, then by the solution and the 6 weight % ammonia spirit parallel-flow precipitations of 250g, the precipitation is filtered, and the Zinc Oxide of fresh clean and the mixed oxide II of gallium oxide after deionized water cyclic washing, are obtained, solution I is mixed into beating with mixed oxide II and obtains slurry III；By the TiO of 1235g weight contents 30%2Colloidal sol is added in slurry III with 17.5g four water-calcium nitrates and 1.59g strontium nitrates, mixing beating, the pH value that slurry is adjusted with dust technology simultaneously is 2.0, obtain slurry IV (solid content 30%), by the slurry spray drying forming, spraying machine inlet temperature is 290 DEG C, 170 DEG C of outlet temperature, then carry out roasting, 600 DEG C of sintering temperature, roasting time 3.5h, obtains microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst, and which is made and consists of (except special identifier all components ratio is atomic ratio)：
35 weight %Fe100Zn20Ga20Ca5Sr0.5Ox+ 65 weight %TiO2。
【Embodiment 7】
Take 367.43g ferric citrates wiring solution-forming soluble in water I；Five nitric hydrate indiums of 892.0g zinc nitrate hexahydrates and 2.93g are dissolved in the water and make solution, then by the solution and the 6 weight % ammonia spirit parallel-flow precipitations of 1860g, the precipitation is filtered, and the Zinc Oxide of fresh clean and the mixed oxide II of Indium sesquioxide. after deionized water cyclic washing, are obtained, solution I is mixed into beating with mixed oxide II and obtains slurry III；By the ZrO of 725g weight contents 40%2The TiO of colloidal sol and 1209g weight contents 30%2It is added in slurry III with 39.33g barium nitrates and 4.5g Cesium hydrate., mixing beating, while the pH value with weak ammonia regulation slurry is 4, obtains slurry IV (solid content 40%), by the slurry spray drying forming, spraying machine inlet temperature is 270 DEG C, and then 160 DEG C of outlet temperature carries out roasting, 480 DEG C of sintering temperature, roasting time 4.5h, obtains microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst, and which is made and consists of (except special identifier all components ratio is atomic ratio)：
30 weight %Fe100Zn200In0.5Ba10Cs2Ox+ 30 weight %ZrO2+ 40 weight %TiO2。
【Embodiment 8】
Take the Fe(NO3)39H2O wiring solution-forming soluble in water I of 606.03g；Tetra- water cadmium nitrates of 925.0g and nine nitric hydrate galliums of 3.13g are dissolved in the water and make solution, then by the solution and the 6 weight % ammonia spirit parallel-flow precipitations of 1860g, the precipitation is filtered, and the Aska-Rid. of fresh clean and the mixed oxide II of gallium oxide after deionized water cyclic washing, are obtained, solution I is mixed into beating with mixed oxide II and obtains slurry III；By the ZrO of 725g weight contents 40%2The TiO of colloidal sol and 1209g weight contents 30%2It is added in slurry III with 38.4g magnesium nitrate hexahydrates and 1.68g potassium hydroxide, mixing beating, the pH value that slurry is adjusted with dust technology simultaneously is 1.3, obtain slurry IV (solid content 40%), by the slurry spray drying forming, spraying machine inlet temperature is 360 DEG C, 220 DEG C of outlet temperature, then carry out roasting, 650 DEG C of sintering temperature, roasting time 4.15h, obtains microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst, and which is made and consists of (except special identifier all components ratio is atomic ratio)：
30 weight %Fe100Cd200Ga0.5Mg10K2Ox+ 30 weight %ZrO2+ 40 weight %TiO2。
【Embodiment 9】
Take the Fe(NO3)39H2O wiring solution-forming soluble in water I of 606.03g；Five nitric hydrate indiums of tetra- water cadmium nitrates of 92.5g and 117.2g are dissolved in the water and make solution, then by the solution and the 6 weight % ammonia spirit parallel-flow precipitations of 450g, the precipitation is filtered, and the Aska-Rid. of fresh clean and the mixed oxide II of Indium sesquioxide. after deionized water cyclic washing, are obtained, solution I is mixed into beating with mixed oxide II and obtains slurry III；By the TiO of 1350g weight contents 30%2It is added in slurry III with 19.2g magnesium nitrate hexahydrates and 1.87g Lithium hydrates and 15% dilute sulfuric acid of 4.83g15 weight, mixing beating, the pH value that slurry is adjusted with dust technology simultaneously is 1, obtain slurry IV (solid content 30%), by the slurry spray drying forming, spraying machine inlet temperature is 270 DEG C, 160 DEG C of outlet temperature, then carry out roasting, 600 DEG C of sintering temperature, roasting time 1h, obtains microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst, and which is made and consists of (except special identifier all components ratio is atomic ratio)：
35 weight %Fe100Cd20In20Mg5Li5.2S0.5Ox+ 65 weight %TiO2。
【Embodiment 10】
Take the Fe(NO3)39H2O wiring solution-forming soluble in water I of 606.03g；It is dissolved in the water 2.23g zinc nitrate hexahydrates and with the five nitric hydrate indiums of 293.12g and makes solution, then by the solution and the 6 weight % ammonia spirit parallel-flow precipitations of 680g, the precipitation is filtered, and the Zinc Oxide of fresh clean and the mixed oxide II of Indium sesquioxide. after deionized water cyclic washing, are obtained, solution I is mixed into beating with mixed oxide II and obtains slurry III；By the ZrO of 62.3g weight contents 40%2It is added in slurry III with 0.38g magnesium nitrate hexahydrates and mixes beating, the pH value that slurry is adjusted with ammonia simultaneously is 5, slurry IV (solid content 15%) is obtained, by the slurry spray drying forming, spraying machine inlet temperature is 380 DEG C, 230 DEG C of outlet temperature, then roasting, 750 DEG C of sintering temperature, roasting time 6h are carried out, microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst is obtained, which is made and consists of (except special identifier all components ratio is atomic ratio)：
90 weight %Fe100Zn0.5In50Mg0.1Ox+ 10 weight %ZrO2。
【Comparative example 1】
Take the Fe(NO3)39H2O wiring solution-forming soluble in water I of 606.03g；2.23g zinc nitrate hexahydrates and nine nitric hydrate galliums of 313.3g are dissolved in the water and make solution, then by the solution and the 6 weight % ammonia spirit parallel-flow precipitations of 700g, the precipitation is filtered, and the Zinc Oxide of fresh clean and the mixed oxide II of gallium oxide after deionized water cyclic washing, are obtained, solution I is mixed into beating with mixed oxide II and obtains slurry III；By the ZrO of 908g weight contents 40%2Colloidal sol is added in slurry III with 0.35g four water-calcium nitrates and 0.042g potassium hydroxide, mixing beating, the pH value that slurry is adjusted with ammonia simultaneously is 5, obtain slurry IV (solid content 15%), by the slurry spray drying forming, spraying machine inlet temperature is 380 DEG C, 230 DEG C of outlet temperature, then carry out roasting, 750 DEG C of sintering temperature, roasting time 6h, obtains microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst, and which is made and consists of (except special identifier all components ratio is atomic ratio)：
5 weight %Fe100Zn0.5Ga50Ca0.1K0.05Ox+ 95 weight %ZrO2。
【Comparative example 2】
Take the Fe(NO3)39H2O wiring solution-forming soluble in water I of 606.03g；892.0g zinc nitrate hexahydrates are dissolved in the water and make solution, then by the solution and the 6 weight % ammonia spirit parallel-flow precipitations of 1860g, the precipitation is filtered, and the Zinc Oxide of fresh clean and the mixed oxide II of gallium oxide after deionized water cyclic washing, are obtained, solution I is mixed into beating with mixed oxide II and obtains slurry III；By the ZrO of 1692g weight contents 40%2Colloidal sol is added in slurry III with 38.4g magnesium nitrate hexahydrates and 4.20g potassium hydroxide, mixing beating, the pH value that slurry is adjusted with dust technology simultaneously is 1, obtain slurry IV (solid content 45%), by the slurry spray drying forming, spraying machine inlet temperature is 200 DEG C, 100 DEG C of outlet temperature, then carry out roasting, 400 DEG C of sintering temperature, roasting time 0.15h, obtains microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst, and which is made and consists of (except special identifier all components ratio is atomic ratio)：
30 weight %Fe100Zn200Mg10K5Ox+ 70 weight %ZrO2。
【Comparative example 3】
Fixed bed catalyst is prepared using the method described in CN 1395993A, its formula is identical with embodiment 1
Obtained is above-mentioned except catalyst carries out Fischer-Tropsch synthesis in addition to comparative example 3 under following reaction conditions, is as a result listed in table 1.
Reducing condition is：
450 DEG C of temperature
Pressure 0.2MPa
50 grams of loaded catalyst
Catalyst loading (reaction volume air speed) 2500 hours-1
Also Primordial Qi H2/ CO=0.25/1
24 hours recovery times
Reaction condition is：
38 millimeters of fluidized-bed reactors of φ
300 DEG C of reaction temperature
Reaction pressure 1.75MPa
50 grams of loaded catalyst
Catalyst loading (reaction volume air speed) 10000 hours-1
Proportioning raw materials (mole) H2/ CO=2/1
By comparative example 3 as described in patent CN 1395993A in fixed bed evaluation analysis the results are shown in Table 1
The evaluation result of 1 embodiment catalyst of table
#The data being reacted to during 2000h
* the data of former patent are selected from.
Claims (10)
1. a kind of GTO catalyst for fluid bed, catalyst in terms of parts by weight, including following components：
A) 10～70 parts of carriers, carrier are at least one in the oxide of Zr or Ti；
B) 30～90 parts of active components, active component contain with atomic ratio measuring, the following compositionss of chemical formula：
Fe100AaBbCcOx
The one kind of A in Zn or Cd；
The one kind of B in Ga or In；
The one kind of C in alkaline-earth metal；
The span of a is 0.5～200.0；
The span of b is 0.1～10.0；
The span of c is 0.1～10.0；
Oxygen atom sums of the x in meet catalyst needed for each element quantivalence.
2. the GTO catalyst for fluid bed according to claim 1, its active component also include element D, and D is that alkali metal is a kind of, and the ratio of D and Fe is with atomic ratio measuring as Fe：D=100：The span of d, d is 0.05～5.0.
3. the GTO catalyst for fluid bed according to claim 1 and 2, it is characterised in that the span of a is 0.8～175.0.
4. the GTO catalyst for fluid bed according to claim 1 and 2, it is characterised in that the span of b is 0.8～45.0.
5. the GTO catalyst for fluid bed according to claim 1 or claim 2, it is characterised in that the span of c is preferably 0.15～9.0.
6. the GTO catalyst for for fluid bed according to claim 1 and 2, it is characterised in that carrier consumption it is optimum for by weight percentage for catalyst weight 15～65%.
7. the GTO catalyst for fluid bed according to claim 2, it is characterised in that the span of d is preferably 0.1～4.5.
8. the preparation method of the GTO catalyst for fluid bed described in claim 1 or 2, comprises the following steps that：
(1) solution I is made by soluble ferric iron salt soluble in water；
(2) by alite with belit is soluble in water makes solution, then the mixed oxide II of A and B is filtrated to get with after alkaline precipitating agent parallel-flow precipitation；
(3) solution I is mixed into beating with mixed oxide II and obtains slurry III；
(4) will be selected from ZrO2Or TiO2In at least one colloidal sol and the hydroxide or saline solution one kind of C and D be added in slurry III, mixing beating, while adding the pH value that acid-base modifier adjusts slurry to be 1～5 to obtain slurry IV, IV solid content of slurry is 15～45 weight %；
(5) slurry IV is sent into into spray dryer spray shaping, then in 400～750 DEG C of roasting temperatures 0.15～6 hour, obtains microsphere shaped iron based catalyst.
9. the preparation method of the GTO catalyst for fluid bed according to claim 8, it is characterised in that the spray shaping condition of catalyst is 200～380 DEG C of inlet temperature, 100～230 DEG C of outlet temperature.
10. the preparation method of the GTO catalyst for fluid bed according to claim 8, it is characterised in that sintering temperature is 450～700 DEG C, roasting time is 0.5～5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510683782.8A CN106607037B (en) | 2015-10-21 | 2015-10-21 | GTO catalyst for fluid bed and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510683782.8A CN106607037B (en) | 2015-10-21 | 2015-10-21 | GTO catalyst for fluid bed and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106607037A true CN106607037A (en) | 2017-05-03 |
| CN106607037B CN106607037B (en) | 2018-05-11 |
Family
ID=58611978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510683782.8A Active CN106607037B (en) | 2015-10-21 | 2015-10-21 | GTO catalyst for fluid bed and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106607037B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109603898A (en) * | 2017-10-17 | 2019-04-12 | 苏州大学 | A kind of catalyst for dehydrogenation of low-carbon paraffin and the method for preparing low-carbon alkene |
| CN111068689A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin by synthesis gas direct method and application thereof |
| CN112619650A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Catalyst for preparing light olefin from synthesis gas and preparation method thereof |
| CN113926457A (en) * | 2020-06-29 | 2022-01-14 | 中国石油化工股份有限公司 | Catalyst for high-temperature Fischer-Tropsch synthesis and preparation method and application thereof |
| CN114643064A (en) * | 2020-12-18 | 2022-06-21 | 中国石油化工股份有限公司 | Microspherical fluidized bed catalyst and preparation method and application thereof |
| US20220288570A1 (en) * | 2021-03-10 | 2022-09-15 | University Of South Florida | Catalyst for syngas conversion to light olefins |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4861802A (en) * | 1988-02-17 | 1989-08-29 | E. I. Du Pont De Nemours And Company | Preparation of low molecular weight olefinic hydrocarbons using a perovskite catalyst |
| CN101757925A (en) * | 2009-12-31 | 2010-06-30 | 浙江工业大学 | Fused iron catalyst for producing light olefins from syngas and preparation method and application thereof |
| CN102452878A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin by synthetic gas one-step technology |
-
2015
- 2015-10-21 CN CN201510683782.8A patent/CN106607037B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4861802A (en) * | 1988-02-17 | 1989-08-29 | E. I. Du Pont De Nemours And Company | Preparation of low molecular weight olefinic hydrocarbons using a perovskite catalyst |
| CN101757925A (en) * | 2009-12-31 | 2010-06-30 | 浙江工业大学 | Fused iron catalyst for producing light olefins from syngas and preparation method and application thereof |
| CN102452878A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin by synthetic gas one-step technology |
Non-Patent Citations (1)
| Title |
|---|
| HIRSA M. TORRES GALVIS等: "Effects of sodium and sulfur on catalytic performance of supported iron catalysts for the Fischer–Tropsch synthesis of lower olefins", 《JOURNAL OF CATALYSIS》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109603898A (en) * | 2017-10-17 | 2019-04-12 | 苏州大学 | A kind of catalyst for dehydrogenation of low-carbon paraffin and the method for preparing low-carbon alkene |
| CN109603898B (en) * | 2017-10-17 | 2021-12-21 | 苏州大学 | Low-carbon alkane dehydrogenation catalyst and method for preparing low-carbon olefin |
| CN111068689A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin by synthesis gas direct method and application thereof |
| CN111068689B (en) * | 2018-10-18 | 2023-04-07 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin by direct synthesis gas method and application thereof |
| CN112619650A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Catalyst for preparing light olefin from synthesis gas and preparation method thereof |
| CN112619650B (en) * | 2019-09-24 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst for preparing light olefin from synthesis gas and preparation method thereof |
| CN113926457A (en) * | 2020-06-29 | 2022-01-14 | 中国石油化工股份有限公司 | Catalyst for high-temperature Fischer-Tropsch synthesis and preparation method and application thereof |
| CN113926457B (en) * | 2020-06-29 | 2024-02-02 | 中国石油化工股份有限公司 | Catalyst for high-temperature Fischer-Tropsch synthesis and preparation method and application thereof |
| CN114643064A (en) * | 2020-12-18 | 2022-06-21 | 中国石油化工股份有限公司 | Microspherical fluidized bed catalyst and preparation method and application thereof |
| CN114643064B (en) * | 2020-12-18 | 2023-11-28 | 中国石油化工股份有限公司 | Microspherical fluidized bed catalyst and preparation method and application thereof |
| US20220288570A1 (en) * | 2021-03-10 | 2022-09-15 | University Of South Florida | Catalyst for syngas conversion to light olefins |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106607037B (en) | 2018-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106607037B (en) | GTO catalyst for fluid bed and preparation method thereof | |
| CN104549296B (en) | Microspheroidal synthesis gas directly prepares catalyst of low-carbon alkene and preparation method thereof | |
| CN104226329B (en) | Catalyst for direct preparation of low carbon olefin from synthesis gas and preparation method thereof | |
| CN102371154B (en) | Iron-based catalyst for synthesizing light hydrocarbon and preparation method thereof | |
| CN103933989B (en) | For the synthesis of the Catalysts and its preparation method of low-carbon alkene | |
| CN106607053B (en) | Synthesis gas directly prepares Fe-Mn series catalysts of low-carbon alkene and preparation method thereof | |
| CN101993707A (en) | Fischer-Tropsch synthesis method for heavy hydrocarbon | |
| CN102453492B (en) | Fischer-Tropsch synthesis method for heavy hydrocarbons | |
| CN106607050B (en) | The fluid catalyst and preparation method thereof of one-step method from syngas producing light olefins | |
| CN104107699B (en) | Ferrum-based catalyst for synthesizing low-carbon alkene and preparation method thereof | |
| CN106607051A (en) | Catalyst for one-step preparation of low-carbon olefin from synthetic gas and preparation method thereof | |
| CN106607061A (en) | Fluidized bed catalyst for preparing low-carbon olefin from synthetic gas through one step method and preparation method of fluidized bed catalyst | |
| CN106607058A (en) | Iron-based catalyst for preparing low-carbon olefin directly from synthesis gas and preparation method of iron-based catalyst | |
| CN102041021B (en) | Method for synthesizing heavy hydrocarbon by fischer-tropsch | |
| CN103962148B (en) | Directly prepare fluid catalyst and the production method thereof of low-carbon alkene for the synthesis of gas | |
| CN102039135B (en) | Fe-based fluidized bed catalyst for Fischer-Tropsch synthesis and preparation method thereof | |
| CN109092321A (en) | The catalyst system of one-step method from syngas producing light olefins | |
| CN106607059B (en) | The Fe-Mn series catalysts and preparation method thereof of low-carbon alkene are directly prepared for synthesis gas | |
| CN111068687B (en) | Catalyst for preparing low-carbon olefin by synthesis gas one-step method and application thereof | |
| CN106607049B (en) | Catalyst of preparation of low carbon olefines by synthetic gas and preparation method thereof | |
| CN103418393A (en) | Catalyst for Fischer-Tropsch synthetic heavy hydrocarbons and preparation method thereof | |
| CN103657678A (en) | Micro-spherical Fe-based Fischer-Tropsch synthesis catalyst as well as preparation method and application thereof | |
| CN103666517A (en) | Method for producing heavy hydrocarbons through Fischer-Tropsch synthesis | |
| CN103657675B (en) | The Catalysts and its preparation method of microspheroidal iron-base fischer-tropsch synthesis | |
| CN103521232A (en) | Micro spherical iron-based Fischer-Tropsch synthesis catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |