CN104549325A - Catalyst for preparing low-carbon olefin from synthesis gas by one-step method, preparation method and application of catalyst - Google Patents
Catalyst for preparing low-carbon olefin from synthesis gas by one-step method, preparation method and application of catalyst Download PDFInfo
- Publication number
- CN104549325A CN104549325A CN201310525090.1A CN201310525090A CN104549325A CN 104549325 A CN104549325 A CN 104549325A CN 201310525090 A CN201310525090 A CN 201310525090A CN 104549325 A CN104549325 A CN 104549325A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oxide
- step method
- light olefins
- gas
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a catalyst for preparing low-carbon olefin from synthesis gas by a one-step method and a preparation method of the catalyst, which are mainly used for solving the problems of low CO conversion rate and low selectivity of low-carbon olefin in the reaction for preparing low-carbon olefin from synthesis gas in the prior art. The catalyst adopted by the invention comprises the following components in percentage by weight: (a) 5-60% of ferrum element or an oxide of the ferrum element; (b) 1-10% of cobalt element or an oxide thereof; (c) 4-20% of at least one element or an oxide thereof selected from strontium or magnesium; (d) 4-20% of at least one element or an oxide thereof selected from molybdenum and zirconium; (e) 1-10% of erbium element or an oxide thereof; and (f) 30-85% of a cocoanut active charcoal carrier. By adopting the technical scheme, the problem is solved well, and the catalyst and the preparation method thereof can be applied to the industrial production for preparing the low-carbon olefin from synthesis gas by using a fixed bed.
Description
Technical field
The present invention relates to a kind of catalyst of one-step method from syngas producing light olefins, the preparation method and its usage of catalyst.
Background technology
Low-carbon alkene refers to that carbon number is less than or equal to the alkene of 4.The low-carbon alkene being representative with ethene, propylene is very important basic organic chemical industry raw material, and along with the quick growth of China's economy, for a long time, supply falls short of demand in low-carbon alkene market.At present, the production of low-carbon alkene mainly adopts the petrochemical industry route of lighter hydrocarbons (ethane, naphtha, light diesel fuel) cracking, due to day by day shortage and the long-term run at high level of crude oil price of Global Oil resource, development low-carbon alkene industrial only dependence petroleum light hydrocarbon is that the tube cracking furnace technique of raw material can run into an increasing raw material difficult problem, and low-carbon alkene production technology and raw material must diversification.The direct preparing low-carbon olefins of one-step method from syngas is exactly that carbon monoxide and hydrogen are under catalyst action, by Fischer-Tropsch synthesis directly obtained carbon number be less than or equal to the process of the low-carbon alkene of 4, this technique without the need to as indirect method technique from synthesis gas through methanol or dimethyl ether, prepare alkene further, simplification of flowsheet, greatly reduces investment.Petroleum resources shortage at home, it is current that external dependence degree is more and more higher, international oil price constantly rises violently, synthesis gas producing olefinic hydrocarbons technique is selected to widen raw material sources, will with crude oil, natural gas, coal and recyclable materials for synthesis gas be produced by raw material, can for providing replacement scheme based on the steam cracking technology aspect of high cost raw material as naphtha.The coal price of the coal resources that China is abundant and relative moderate is that Development of Coal oil refining and application preparation of low carbon olefines by synthetic gas technique provide the good market opportunity.And near the abundant oil gas field of Natural Gas In China, if Gas Prices is cheap, be also the fabulous opportunity of application preparation of low carbon olefines by synthetic gas technique.If can utilize coal and the natural gas resource of China's abundant, by gas making producing synthesis gas (gaseous mixture of carbon monoxide and hydrogen), the substitute energy source for petroleum technology of development preparation of low carbon olefines by synthetic gas, will be significant to energy problem of solution China.
One-step method from syngas producing light olefins technique functions comes from traditional Fischer-Tropsch synthesis, and the carbon number distribution of traditional Fischer-Tropsch synthetic defers to ASF distribution, and it is selective that each hydro carbons all has theoretical maximum, as C
2-C
4the selective of cut is up to 57%, gasoline fraction (C
5-C
11) be selectively up to 48%.Chain growth probability α value is larger, product heavy hydrocarbon selective larger.Once α value determines, the selective of whole synthetic product just determines, and chain growth probability α value depends on catalyst composition, granularity and reaction condition etc.In recent years, it is found that due to alhpa olefin on a catalyst adsorb the alkene secondary response caused again, product distribution deviates from desirable ASF and distributes.F-T synthesis is a kind of strong exothermal reaction, and a large amount of reaction heat will impel catalyst carbon deposit to react more easily generation methane and low-carbon alkanes, cause selectivity of light olefin significantly to decline; Secondly, it is unfavorable that complicated kinetic factor also causes to selectivity synthesis low-carbon alkene; The ASF distribution of Fischer-Tropsch synthetic limits the selective of synthesizing low-carbon alkene.The catalyst mainly iron catalyst series of F-T synthesis gas producing light olefins, in order to improve the selective of the direct preparing low-carbon olefins of synthesis gas, physics and chemistry modification can be carried out to fischer-tropsch synthetic catalyst, as the pore passage structure utilizing molecular sieve suitable, be conducive to low-carbon alkene to spread in time and leave metal active centres, suppress the secondary response of low-carbon alkene; Improve metal ion dispersed, also have good olefine selective; Support-metal strong interaction changes also can improve selectivity of light olefin; Add suitable transition metal, can enhanced activity component and the bond energy of carbon, suppress methane generation, raising selectivity of light olefin; Add electronics accelerating auxiliaries, impel CO chemisorbed heat to increase, adsorbance also increases, and hydrogen adsorptive capacity reduces, and result selectivity of light olefin increases; Eliminate catalyst acid center, the secondary response of low-carbon alkene can be suppressed, improve that it is selective.By Support effect and some transition metal promoter of interpolation and the alkali metal promoter of catalyst carrier, obviously can improve catalyst performance, develop the fischer-tropsch synthetic catalyst of the novel high-activity high selectivity producing light olefins with the non-ASF distribution of product.
One-step method from syngas directly produces low-carbon alkene, has become one of study hotspot of fischer-tropsch synthetic catalyst exploitation.In patent CN1083415A disclosed in Dalian Chemiclophysics Inst., Chinese Academy of Sciences, by iron-Mn catalyst system that the IIA race alkali metal oxides such as MgO or silica-rich zeolite molecular sieve (or phosphorus aluminium zeolite) support, auxiliary agent is made with highly basic K or Cs ion, be 1.0 ~ 5.0MPa in preparation of low carbon olefines by synthetic gas reaction pressure, at reaction temperature 300 ~ 400 DEG C, higher activity (CO conversion ratio 90%) and selective (selectivity of light olefin 66%) can be obtained.But this catalyst preparation process is complicated, and particularly the shaping process cost of the preparation of carrier zeolite molecular sieve is higher, is unfavorable for suitability for industrialized production.In the number of patent application 01144691.9 that Beijing University of Chemical Technology declares, laser pyrolysis processes is adopted to prepare in conjunction with solid phase reaction combination technique with Fe
3c is that main Fe base nano-catalyst is applied to preparation of low carbon olefines by synthetic gas, and achieves good catalytic effect, and because needs use laser pyrolysis technology, preparation technology is more loaded down with trivial details, and raw material adopts Fe (CO)
5, catalyst cost is very high, industrialization difficulty.In the patent ZL03109585.2 that Beijing University of Chemical Technology declares, vacuum impregnation technology is adopted to prepare the Fe/ activated-carbon catalyst for auxiliary agent such as manganese, copper, zinc silicon, potassium for the synthesis of gas reaction for preparing light olefins, under the condition circulated without unstripped gas, CO conversion ratio 96%, low-carbon alkene in hydrocarbon selective 68%.The molysite that this catalyst preparing uses and auxiliary agent manganese salt are more expensive and more insoluble ferric oxalate and manganese acetate, simultaneously with ethanol as solvent, and just inevitable cost of material and the running cost increasing catalyst preparation process.For reducing the cost of catalyst further; in its number of patent application 200710063301.9; catalyst adopts common medicine and reagent preparation, and the molysite of use is ferric nitrate, and manganese salt is manganese nitrate; sylvite is potash; active carbon is coconut husk charcoal, can must carry out high-temperature roasting and Passivation Treatment by catalyst, need special installation under flowing nitrogen protection; preparation process is complicated, and cost is higher.And the CO conversion ratio of above-mentioned catalyst in fixed bed reaction and selectivity of light olefin all lower.
Summary of the invention
Technical problem to be solved by this invention is that in prior art, synthesis gas produces the problem that in low-carbon alkene technology, in CO low conversion rate and product, selectivity of light olefin is low, a kind of method of new one-step method from syngas producing light olefins is provided, the method uses novel fixed bed F-T synthesis producing light olefins iron-cobalt bimetallic catalyst, has the advantage that in CO conversion ratio height and product, selectivity of light olefin is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst for the synthesis of gas one-step method producing light olefins, comprises following component by weight percentage:
A) 5 ~ 60% ferro element or its oxide;
B) 1 ~ 10% cobalt element or its oxide;
C) 4 ~ 20% be selected from least one element in strontium and magnesium or its oxide;
D) 4 ~ 20% be selected from least one element in molybdenum and zirconium or its oxide;
E) 1 ~ 10% er element or its oxide;
F) the coconut activated high-area carbon of 30 ~ 85%.
In technique scheme, the preferred version of the oxide of iron is di-iron trioxide, and the preferable range of content is 10 ~ 50% by weight percentage; The preferred version of the oxide of cobalt is cobaltosic oxide, and the preferable range of content is 1 ~ 5% by weight percentage; The preferred version of the oxide of strontium and magnesium is respectively strontium oxide strontia and magnesia, and the preferable range of content is 5 ~ 15% by weight percentage; The preferred version of the oxide of molybdenum and zirconium is respectively molybdenum oxide and zirconia, and the preferable range of content is 5 ~ 15% by weight percentage; The preferred version of the oxide of erbium is oxidation bait, and the preferable range of content is 1 ~ 5% by weight percentage.The preferred version of carrier is coconut activated high-area carbon, and the preferable range of content is 40 ~ 70% by weight percentage.
In technique scheme, the preparation method of one-step method from syngas producing light olefins catalyst used, comprises the following steps:
(1) coconut activated high-area carbon washed for acid washing water is carried out ultrasonic and dry process, make carrier H stand-by;
(2) by molysite, cobalt salt, magnesium salts or strontium salt, molybdenum salt or zirconates, and erbium salt, make mixed solution I in water-soluble deionized water;
(3) under vacuum 1 ~ 80 kPa condition, above-mentioned mixed solution I to be impregnated on the carrier H that handles well in (1) step to obtain catalyst precarsor J;
(4) by catalyst precarsor J, after drying roasting, required catalyst is obtained.
In technique scheme, the preferable range of the sintering temperature of catalyst precarsor is 450 ~ 750 DEG C, and the preferable range of roasting time is 1.0 ~ 4.5 hours.
In technique scheme, described synthesis gas produces the method for low-carbon alkene, take synthesis gas as raw material, H
2be 1 ~ 3 with the mol ratio of CO, be 250 ~ 400 DEG C in reaction temperature, reaction pressure is 1.0 ~ 3.0Mpa, and feed gas volume air speed is 500 ~ 5000h
-1condition under, unstripped gas and described catalyst exposure react and generate containing C
2~ C
4alkene.
The preprocess method of carrier cocoanut active charcoal is dust technology and deionized water carrying out washing treatment, is all the conventional preprocess method of this area, and object is the impurity in order to remove coconut activated carbon surface.
The catalyst that the inventive method adopts is prepared by vacuum impregnation technology, and active component and auxiliary agent high uniformity can be made to be scattered in cocoanut active charcoal carrier surface, increases the quantity being exposed to the active sites of carrier surface, improves the conversion ratio of CO.
Fischer-Tropsch synthesis second active component Co is introduced in the catalyst that the inventive method adopts, alkaline-earth metal Sr or Mg, transition metal M o or Zr, and lanthanide series metal Er is as catalyst promoter, can the electron valence state of modulation active component Fe, thus be conducive to improving the CO conversion ratio of catalyst and the selective of low-carbon alkene.Particularly introduce the second active component Co and lanthanide series metal Er, not only can the electron valence state of modulation active component, and strengthen the interaction strength of catalyst activity component and carrier, thus be conducive to the selectivity of light olefin improving catalyst.
The reaction condition of one-step method from syngas producing light olefins is as follows: with H
2with CO composition synthesis gas be raw material, H
2be 1 ~ 3 with the mol ratio of CO, be 250 ~ 400 DEG C in reaction temperature, reaction pressure is 1.0 ~ 3.0Mpa, and feed gas volume air speed is 500 ~ 5000h
-1condition under, unstripped gas and above-mentioned catalyst exposure.Achieve good technique effect: CO conversion ratio can reach 99.9%, improve 3.9% than prior art; Selective in hydrocarbon of low-carbon alkene reaches 77.5%, improves 9.5%, the results are shown in subordinate list in more detail than prior art.
The present invention is described further for the following examples, and protection scope of the present invention is not by the restriction of these embodiments.
Detailed description of the invention
[embodiment 1]
Take 100.0 gram of 60 ~ 80 object cocoanut active charcoal and carry out dust technology and deionized water carrying out washing treatment, make carrier H at 120 DEG C of dry 4h stand-by; By 101.2 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 18.4 grams of strontium nitrates, 12.3 gram of four hydration ammonium heptamolybdate, 7.0 gram of five nitric hydrate erbium, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 55.0 grams of coconut activated high-area carbon H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 120 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 3h, namely obtains the catalyst of required one-step method from syngas producing light olefins.Obtained catalyst, comprises following component: 20% Fe
2o
3, 3% Co
3o
4, 9% SrO, 10% MoO
3, 3% Er
2o
3, 55% C (cocoanut active charcoal, lower same); Obtained catalyst carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result lists in table 1.
[embodiment 2]
Take 100.0 gram of 60 ~ 80 object cocoanut active charcoal and carry out dust technology and deionized water carrying out washing treatment, make carrier H at 120 DEG C of dry 4h stand-by; By 303.6 grams of Fe(NO3)39H2Os, 3.6 grams of cabaltous nitrate hexahydrates, 8.2 grams of strontium nitrates, 4.9 gram of four hydration ammonium heptamolybdate, 2.3 gram of five nitric hydrate erbium, be dissolved in 20.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 30.0 grams of coconut activated high-area carbon H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 120 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 3h, namely obtains the catalyst of required one-step method from syngas producing light olefins.Obtained catalyst, comprises following component: 60% Fe
2o
3, 1% Co
3o
4, 4% SrO, 4% MoO
3, 1% Er
2o
3, 30% C; Obtained catalyst carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result lists in table 1.
[embodiment 3]
Take 100.0 gram of 60 ~ 80 object cocoanut active charcoal and carry out dust technology and deionized water carrying out washing treatment, make carrier H at 120 DEG C of dry 4h stand-by; By 25.3 grams of Fe(NO3)39H2Os, 3.6 grams of cabaltous nitrate hexahydrates, 8.2 grams of strontium nitrates, 4.9 gram of four hydration ammonium heptamolybdate, 2.3 gram of five nitric hydrate erbium, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 85.0 grams of coconut activated high-area carbon H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 120 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 3h, namely obtains the catalyst of required one-step method from syngas producing light olefins.Obtained catalyst, comprises following component: 5% Fe
2o
3, 1% Co
3o
4, 4% SrO, 4% MoO
3, 1% Er
2o
3, 85% C; Obtained catalyst carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result lists in table 1.
[embodiment 4]
Take 100.0 gram of 60 ~ 80 object cocoanut active charcoal and carry out dust technology and deionized water carrying out washing treatment, make carrier H at 120 DEG C of dry 4h stand-by; By 50.6 grams of Fe(NO3)39H2Os, 36.3 grams of cabaltous nitrate hexahydrates, 40.8 grams of strontium nitrates, 24.5 gram of four hydration ammonium heptamolybdate, 23.2 gram of five nitric hydrate erbium, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 30.0 grams of coconut activated high-area carbon H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 120 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 3h, namely obtains the catalyst of required one-step method from syngas producing light olefins.Obtained catalyst, comprises following component: 10% Fe
2o
3, 10% Co
3o
4, 20% SrO, 20% MoO
3, 10% Er
2o
3, 30% C; Obtained catalyst carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result lists in table 1.
[embodiment 5]
Take 100.0 gram of 60 ~ 80 object cocoanut active charcoal and carry out dust technology and deionized water carrying out washing treatment, make carrier H at 120 DEG C of dry 4h stand-by; By 253.0 grams of Fe(NO3)39H2Os, 18.1 grams of cabaltous nitrate hexahydrates, 10.2 grams of strontium nitrates, 6.1 gram of four hydration ammonium heptamolybdate, 11.6 gram of five nitric hydrate erbium, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 30.0 grams of coconut activated high-area carbon H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 120 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 3h, namely obtains the catalyst of required one-step method from syngas producing light olefins.Obtained catalyst, comprises following component: 50% Fe
2o
3, 5% Co
3o
4, 5% SrO, 5% MoO
3, 5% Er
2o
3, 30% C; Obtained catalyst carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result lists in table 1.
[embodiment 6]
Take 100.0 gram of 60 ~ 80 object cocoanut active charcoal and carry out dust technology and deionized water carrying out washing treatment, make carrier H at 120 DEG C of dry 4h stand-by; By 101.2 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 30.6 grams of strontium nitrates, 18.4 gram of four hydration ammonium heptamolybdate, 16.2 gram of five nitric hydrate erbium, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 40.0 grams of coconut activated high-area carbon H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 120 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 3h, namely obtains the catalyst of required one-step method from syngas producing light olefins.Obtained catalyst, comprises following component: 20% Fe
2o
3, 3% Co
3o
4, 15% SrO, 15% MoO
3, 7% Er
2o
3, 40% C; Obtained catalyst carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result lists in table 1.
[embodiment 7]
Take 100.0 gram of 60 ~ 80 object cocoanut active charcoal and carry out dust technology and deionized water carrying out washing treatment, make carrier H at 120 DEG C of dry 4h stand-by; By 91.1 grams of Fe(NO3)39H2Os, 3.6 grams of cabaltous nitrate hexahydrates, 10.2 grams of strontium nitrates, 6.1 gram of four hydration ammonium heptamolybdate, 2.3 gram of five nitric hydrate erbium, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 70.0 grams of coconut activated high-area carbon H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 120 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 3h, namely obtains the catalyst of required one-step method from syngas producing light olefins.Obtained catalyst, comprises following component: 18% Fe
2o
3, 1% Co
3o
4, 5% SrO, 5% MoO
3, 1% Er
2o
3, 70% C; Obtained catalyst carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result lists in table 1.
[embodiment 8]
Take 100.0 gram of 60 ~ 80 object cocoanut active charcoal and carry out dust technology and deionized water carrying out washing treatment, make carrier H at 120 DEG C of dry 4h stand-by; By 96.1 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 18.4 grams of strontium nitrates, 12.3 gram of four hydration ammonium heptamolybdate, 7.0 gram of five nitric hydrate erbium, 2.1 grams of potassium nitrate, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 55.0 grams of coconut activated high-area carbon H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 120 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 3h, namely obtains the catalyst of required one-step method from syngas producing light olefins.Obtained catalyst, comprises following component: 19% Fe
2o
3, 3% Co
3o
4, 9% SrO, 10% MoO
3, 3% Er
2o
3, 1%K
2o, 55% C; Obtained catalyst carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result lists in table 1.
[embodiment 9]
Take 100.0 gram of 60 ~ 80 object cocoanut active charcoal and carry out dust technology and deionized water carrying out washing treatment, make carrier H at 120 DEG C of dry 4h stand-by; By 101.2 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 57.3 grams of magnesium nitrate hexahydrates, 12.3 gram of four hydration ammonium heptamolybdate, 7.0 gram of five nitric hydrate erbium, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 55.0 grams of coconut activated high-area carbon H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 120 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 3h, namely obtains the catalyst of required one-step method from syngas producing light olefins.Obtained catalyst, comprises following component: 20% Fe
2o
3, 3% Co
3o
4, 9% MgO, 10% MoO
3, 3% Er
2o
3, 55% C; Obtained catalyst carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result lists in table 1.
[embodiment 10]
Take 100.0 gram of 60 ~ 80 object cocoanut active charcoal and carry out dust technology and deionized water carrying out washing treatment, make carrier H at 120 DEG C of dry 4h stand-by; By 101.2 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 18.4 grams of strontium nitrates, 34.8 gram of five nitric hydrate zirconium, 7.0 gram of five nitric hydrate erbium, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 55.0 grams of coconut activated high-area carbon H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 120 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 3h, namely obtains the catalyst of required one-step method from syngas producing light olefins.Obtained catalyst, comprises following component: 20% Fe
2o
3, 3% Co
3o
4, 9% SrO, 10% ZrO
2, 3% Er
2o
3, 55% C; Obtained catalyst carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result lists in table 1.
[embodiment 11]
Take 100.0 gram of 60 ~ 80 object cocoanut active charcoal and carry out dust technology and deionized water carrying out washing treatment, make carrier H at 120 DEG C of dry 4h stand-by; By 101.2 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 57.3 grams of magnesium nitrate hexahydrates, 34.8 gram of five nitric hydrate zirconium, 7.0 gram of five nitric hydrate erbium, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 55.0 grams of coconut activated high-area carbon H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 120 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 3h, namely obtains the catalyst of required one-step method from syngas producing light olefins.Obtained catalyst, comprises following component: 20% Fe
2o
3, 3% Co
3o
4, 9% MgO, 10% ZrO
2, 3% Er
2o
3, 55% C; Obtained catalyst carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result lists in table 1.
[embodiment 12]
Take 100.0 gram of 60 ~ 80 object cocoanut active charcoal and carry out dust technology and deionized water carrying out washing treatment, make carrier H at 120 DEG C of dry 4h stand-by; By 101.2 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 18.4 grams of strontium nitrates, 12.3 gram of four hydration ammonium heptamolybdate, 7.0 gram of five nitric hydrate erbium, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 55.0 grams of coconut activated high-area carbon H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 120 DEG C of conditions, then carries out roasting, sintering temperature 450 DEG C, roasting time 6h, namely obtains the catalyst of required one-step method from syngas producing light olefins.Obtained catalyst, comprises following component: 20% Fe
2o
3, 3% Co
3o
4, 9% SrO, 10% MoO
3, 3% Er
2o
3, 55% C; Obtained catalyst carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result lists in table 1.
[embodiment 13]
Take 100.0 gram of 60 ~ 80 object cocoanut active charcoal and carry out dust technology and deionized water carrying out washing treatment, make carrier H at 120 DEG C of dry 4h stand-by; By 101.2 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 18.4 grams of strontium nitrates, 12.3 gram of four hydration ammonium heptamolybdate, 7.0 gram of five nitric hydrate erbium, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 60.0 grams of coconut activated high-area carbon H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 120 DEG C of conditions, then carries out roasting, sintering temperature 700 DEG C, roasting time 1h, namely obtains the catalyst of required one-step method from syngas producing light olefins.Obtained catalyst, comprises following component: 20% Fe
2o
3, 3% Co
3o
4, 9% SrO, 10% MoO
3, 3% Er
2o
3, 55% C; Obtained catalyst carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result lists in table 1.
[embodiment 14]
The catalyst that Example 1 is obtained, other are constant, only change reaction condition, and carry out one-step method from syngas producing light olefins, experimental result lists in table 2.
[comparative example 1]
Take 100.0 gram of 60 ~ 80 object cocoanut active charcoal and carry out dust technology and deionized water carrying out washing treatment, make carrier H at 120 DEG C of dry 4h stand-by; By 115.9 grams of Fe(NO3)39H2Os, 0.4 gram of cabaltous nitrate hexahydrate, 18.4 grams of strontium nitrates, 12.3 gram of four hydration ammonium heptamolybdate, 7.0 gram of five nitric hydrate erbium, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 55.0 grams of coconut activated high-area carbon H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 120 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 3h, namely obtains the catalyst of required one-step method from syngas producing light olefins.Obtained catalyst, comprises following component: 22.9% Fe
2o
3, 0.1% Co
3o
4, 9% SrO, 10% MoO
3, 3% Er
2o
3, 55% C; Obtained catalyst carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result lists in table 1.
[comparative example 2]
Take 100.0 gram of 60 ~ 80 object cocoanut active charcoal and carry out dust technology and deionized water carrying out washing treatment, make carrier H at 120 DEG C of dry 4h stand-by; By 101.2 grams of Fe(NO3)39H2Os, 43.5 grams of cabaltous nitrate hexahydrates, 18.4 grams of strontium nitrates, 12.3 gram of four hydration ammonium heptamolybdate, 7.0 gram of five nitric hydrate erbium, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 46.0 grams of coconut activated high-area carbon H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 120 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 3h, namely obtains the catalyst of required one-step method from syngas producing light olefins.Obtained catalyst, comprises following component: 20% Fe
2o
3, 12% Co
3o
4, 9% SrO, 10% MoO
3, 3% Er
2o
3, 46% C; Obtained catalyst carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result lists in table 1.
[comparative example 3]
Take 100.0 gram of 60 ~ 80 object cocoanut active charcoal and carry out dust technology and deionized water carrying out washing treatment, make carrier H at 120 DEG C of dry 4h stand-by; By 115.9 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 18.4 grams of strontium nitrates, 12.3 gram of four hydration ammonium heptamolybdate, 0.23 gram of five nitric hydrate erbium, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 55.0 grams of coconut activated high-area carbon H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 120 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 3h, namely obtains the catalyst of required one-step method from syngas producing light olefins.Obtained catalyst, comprises following component: 22.9% Fe
2o
3, 3% Co
3o
4, 9% SrO, 10% MoO
3, 0.1% Er
2o
3, 55% C; Obtained catalyst carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result lists in table 1.
[comparative example 4]
Take 100.0 gram of 60 ~ 80 object cocoanut active charcoal and carry out dust technology and deionized water carrying out washing treatment, make carrier H at 120 DEG C of dry 4h stand-by; By 101.2 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 18.4 grams of strontium nitrates, 12.3 gram of four hydration ammonium heptamolybdate, 27.8 gram of five nitric hydrate erbium, be dissolved in 35.0 grams of deionized waters and make mixed solution I; Under the condition of vacuum 80kPa, above-mentioned mixed solution I to be impregnated on 46.0 grams of coconut activated high-area carbon H prepared to obtain catalyst precarsor J; The catalyst precarsor J flooded is dry under 120 DEG C of conditions, then carries out roasting, sintering temperature 600 DEG C, roasting time 3h, namely obtains the catalyst of required one-step method from syngas producing light olefins.Obtained catalyst, comprises following component: 20% Fe
2o
3, 3% Co
3o
4, 9% SrO, 10% MoO
3, 12% Er
2o
3, 46% C; Obtained catalyst carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result lists in table 1.
The reducing condition of above-described embodiment and comparative example is:
Temperature 450 DEG C
Pressure normal pressure
Loaded catalyst 3 ml
Catalyst loading 1000 hours
-1
Reducing gases H
2
8 hours recovery times
Reaction condition is:
φ 8 millimeters of fixed bed reactors
Reaction temperature 360 DEG C
Reaction pressure 1.8MPa
Loaded catalyst 3 ml
Catalyst loading 1000 hours
-1
Pulp furnish (mole) H
2/ CO=1.5/1
Table 1
Table 2
* the appreciation condition of change compared with the condition described in table 1.
Claims (10)
1., for the synthesis of a catalyst for gas one-step method producing light olefins, comprise following component by weight percentage:
A) 5 ~ 60% ferro element or its oxide;
B) 1 ~ 10% cobalt element or its oxide;
C) 4 ~ 20% be selected from least one element in strontium and magnesium or its oxide;
D) 4 ~ 20% be selected from least one element in molybdenum and zirconium or its oxide;
E) 1 ~ 10% er element or its oxide;
F) the coconut activated high-area carbon of 30 ~ 85%.
2. the catalyst for the synthesis of gas one-step method producing light olefins according to claim 1, is characterized in that the oxide of iron in described catalyst is di-iron trioxide, and in catalyst weight percent, content is 10 ~ 50%.
3. the catalyst for the synthesis of gas one-step method producing light olefins according to claim 1, is characterized in that the oxide of cobalt in described catalyst is cobaltosic oxide, and in catalyst weight percent, content is 1 ~ 5%.
4. the catalyst for the synthesis of gas one-step method producing light olefins according to claim 1, is characterized in that the oxide of strontium and magnesium in described catalyst is respectively strontium oxide strontia and magnesia, and in catalyst weight percent, content is 5 ~ 15%.
5. the catalyst for the synthesis of gas one-step method producing light olefins according to claim 1, is characterized in that the oxide of molybdenum and zirconium in described catalyst is respectively molybdenum oxide and zirconia, and in catalyst weight percent, content is 5 ~ 15%.
6. the catalyst for the synthesis of gas one-step method producing light olefins according to claim 1, is characterized in that the oxide of erbium in described catalyst is erbium oxide, and in catalyst weight percent, content is 1 ~ 5%.
7. the catalyst for the synthesis of gas one-step method producing light olefins according to claim 1, is characterized in that coconut activated high-area carbon in described catalyst, and in catalyst weight percent, content is 40 ~ 70%.
8. the preparation method of the catalyst for the synthesis of gas one-step method producing light olefins described in any one of claim 1 ~ 7, comprises the following steps:
(1) coconut activated high-area carbon washed for acid washing water is carried out drying process, make carrier H stand-by;
(2) by molysite, cobalt salt, strontium salt or magnesium salts, molybdenum salt or zirconates, and erbium salt, make mixed solution I in water-soluble deionized water;
(3) under vacuum 1 ~ 80 kPa condition, above-mentioned mixed solution I to be impregnated on the carrier H that handles well in (1) step to obtain catalyst precarsor J;
(4) by catalyst precarsor J, after drying roasting, required catalyst is obtained.
9. the preparation method for the synthesis of gas one-step method producing light olefins catalyst according to claim 8, is characterized in that the sintering temperature of catalyst precarsor is 450 ~ 700 DEG C, roasting time 1.0 ~ 6.0 hours.
10. a method for one-step method from syngas producing light olefins take synthesis gas as raw material, H
2be 1 ~ 3 with the mol ratio of CO, be 250 ~ 400 DEG C in reaction temperature, reaction pressure is 1.0 ~ 3.0Mpa, and feed gas volume air speed is 500 ~ 5000h
-1condition under, unstripped gas and the catalyst exposure described in any one of claim 1 ~ 7 react and generate containing C
2~ C
4alkene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310525090.1A CN104549325B (en) | 2013-10-28 | 2013-10-28 | Catalyst for preparing low-carbon olefin from synthesis gas by one-step method, preparation method and application of catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310525090.1A CN104549325B (en) | 2013-10-28 | 2013-10-28 | Catalyst for preparing low-carbon olefin from synthesis gas by one-step method, preparation method and application of catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104549325A true CN104549325A (en) | 2015-04-29 |
| CN104549325B CN104549325B (en) | 2017-02-15 |
Family
ID=53067030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310525090.1A Active CN104549325B (en) | 2013-10-28 | 2013-10-28 | Catalyst for preparing low-carbon olefin from synthesis gas by one-step method, preparation method and application of catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104549325B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498798A (en) * | 2015-12-11 | 2016-04-20 | 中国科学院上海高等研究院 | Catalyst for directly converting synthesis gas into long-chain alkene by one-step method |
| CN106345514A (en) * | 2016-07-29 | 2017-01-25 | 厦门大学 | Catalyst for preparing low-carbon olefins by one-step conversion of synthetic gas and preparation method thereof |
| CN109012676A (en) * | 2018-08-16 | 2018-12-18 | 山东东岳化工有限公司 | A kind of catalyst and the preparation method and application thereof preparing HF hydrocarbon for hydrofluoroalkane gas phase removal HF |
| CN109092317A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | The catalyst system of direct preparation of low carbon olefines by synthetic gas |
| CN109304216A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | The catalyst of one-step method from syngas production low-carbon alkene |
| CN109651033A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The method of fixed bed preparing low-carbon olefins |
| CN110639486A (en) * | 2018-06-27 | 2020-01-03 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas and application of catalyst in preparation of low-carbon olefin from synthesis gas |
| CN115518647A (en) * | 2021-06-24 | 2022-12-27 | 中国石油化工股份有限公司 | Catalyst for producing low-carbon olefin by using fixed bed synthesis gas and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4584323A (en) * | 1983-12-14 | 1986-04-22 | Exxon Research And Engineering Co. | Fischer-Tropsch hydrocarbon synthesis with copper promoted iron/cobalt spinel catalyst |
| FR2571981A1 (en) * | 1984-10-23 | 1986-04-25 | Elf Aquitaine | Catalyst system for the production of hydrocarbons which are rich in light olefins from carbon monoxide and hydrogen |
| CN101049569A (en) * | 2007-05-11 | 2007-10-10 | 上海兖矿能源科技研发有限公司 | Method for deoxidizing and synthesizing hydrocarbon of molten iron, cobalt catalyst in use for Fischer - Tropsch synthesis |
| CN101219384A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Catalyst for reaction of one-step conversion into low carbon olefin hydrocarbon with synthesis gas |
| CN101480614A (en) * | 2009-01-05 | 2009-07-15 | 北京化工大学 | Fe/pressed active carbon catalyst and preparation method thereof |
| CN102292154A (en) * | 2008-12-08 | 2011-12-21 | Sasol技术股份有限公司 | Olefin selective FT catalyst composition and preparation thereof |
| CN103331171A (en) * | 2013-07-08 | 2013-10-02 | 华东理工大学 | Preparation method and applications of catalyst used for preparing light olefin from synthesis gas |
-
2013
- 2013-10-28 CN CN201310525090.1A patent/CN104549325B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4584323A (en) * | 1983-12-14 | 1986-04-22 | Exxon Research And Engineering Co. | Fischer-Tropsch hydrocarbon synthesis with copper promoted iron/cobalt spinel catalyst |
| FR2571981A1 (en) * | 1984-10-23 | 1986-04-25 | Elf Aquitaine | Catalyst system for the production of hydrocarbons which are rich in light olefins from carbon monoxide and hydrogen |
| CN101219384A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Catalyst for reaction of one-step conversion into low carbon olefin hydrocarbon with synthesis gas |
| CN101049569A (en) * | 2007-05-11 | 2007-10-10 | 上海兖矿能源科技研发有限公司 | Method for deoxidizing and synthesizing hydrocarbon of molten iron, cobalt catalyst in use for Fischer - Tropsch synthesis |
| CN102292154A (en) * | 2008-12-08 | 2011-12-21 | Sasol技术股份有限公司 | Olefin selective FT catalyst composition and preparation thereof |
| CN101480614A (en) * | 2009-01-05 | 2009-07-15 | 北京化工大学 | Fe/pressed active carbon catalyst and preparation method thereof |
| CN103331171A (en) * | 2013-07-08 | 2013-10-02 | 华东理工大学 | Preparation method and applications of catalyst used for preparing light olefin from synthesis gas |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498798A (en) * | 2015-12-11 | 2016-04-20 | 中国科学院上海高等研究院 | Catalyst for directly converting synthesis gas into long-chain alkene by one-step method |
| CN106345514A (en) * | 2016-07-29 | 2017-01-25 | 厦门大学 | Catalyst for preparing low-carbon olefins by one-step conversion of synthetic gas and preparation method thereof |
| CN106345514B (en) * | 2016-07-29 | 2018-11-13 | 厦门大学 | A kind of catalyst and preparation method thereof of one step of synthesis gas conversion producing light olefins |
| CN109092317A (en) * | 2017-06-21 | 2018-12-28 | 中国石油化工股份有限公司 | The catalyst system of direct preparation of low carbon olefines by synthetic gas |
| CN109092317B (en) * | 2017-06-21 | 2021-03-26 | 中国石油化工股份有限公司 | Catalyst system for preparing low-carbon olefin by directly synthesizing gas |
| CN109304216A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | The catalyst of one-step method from syngas production low-carbon alkene |
| CN109651033B (en) * | 2017-10-10 | 2021-08-03 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin by fixed bed |
| CN109651033A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The method of fixed bed preparing low-carbon olefins |
| CN110639486A (en) * | 2018-06-27 | 2020-01-03 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas and application of catalyst in preparation of low-carbon olefin from synthesis gas |
| CN110639486B (en) * | 2018-06-27 | 2022-07-12 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas and application of catalyst in preparation of low-carbon olefin from synthesis gas |
| CN109012676A (en) * | 2018-08-16 | 2018-12-18 | 山东东岳化工有限公司 | A kind of catalyst and the preparation method and application thereof preparing HF hydrocarbon for hydrofluoroalkane gas phase removal HF |
| CN109012676B (en) * | 2018-08-16 | 2021-07-20 | 山东东岳化工有限公司 | Catalyst for preparing hydrofluoroolefin by removing HF from hydrofluoroalkane gas phase, and preparation method and application thereof |
| CN115518647A (en) * | 2021-06-24 | 2022-12-27 | 中国石油化工股份有限公司 | Catalyst for producing low-carbon olefin by using fixed bed synthesis gas and preparation method and application thereof |
| CN115518647B (en) * | 2021-06-24 | 2023-08-08 | 中国石油化工股份有限公司 | Catalyst for producing low-carbon olefin by fixed bed synthesis gas and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104549325B (en) | 2017-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104148106B (en) | Synthesis gas produces catalyst of low-carbon alkene and preparation method thereof | |
| CN104549325B (en) | Catalyst for preparing low-carbon olefin from synthesis gas by one-step method, preparation method and application of catalyst | |
| CN106607043B (en) | Ferrum-based catalyst and its preparation method and application | |
| CN103521253B (en) | The catalyst of one-step method from syngas producing light olefins and preparation method | |
| CN104437511B (en) | Catalyst for producing light olefins by fixed bed and preparation method for catalyst for producing light olefins by fixed bed | |
| CN104437532B (en) | Fixed bed producing light olefins catalyst, preparation method and its usage | |
| CN104549352B (en) | The catalyst and its application method of synthesis gas production low-carbon alkene | |
| CN107913729B (en) | Composite catalyst and preparation method thereof | |
| CN105562026B (en) | Ferrum-based catalyst of sulfur-bearing and its preparation method and application | |
| CN105435801B (en) | Load typed iron catalyst and its preparation method and application | |
| CN104549342A (en) | Iron catalyst for preparing light olefins by use of synthesis gas and preparation method of iron catalyst | |
| CN106607048B (en) | The method of fixed bed production low-carbon alkene | |
| CN104437524B (en) | Iron-based catalyst for preparing low-carbon alkane as well as preparation method and using method of iron-based catalyst for preparing low-carbon alkane | |
| CN107913718A (en) | The ferrum-based catalyst of the direct synthesizing low-carbon alkene of synthesis gas | |
| CN106607047A (en) | Iron-based catalyst for preparing low-carbon olefins from synthesis gas and application of iron-based catalyst | |
| CN105582936A (en) | Catalyst used for preparing light olefin with sintered synthetic gas, and preparation method thereof | |
| CN103521241A (en) | Catalyst for direct conversion from synthesis gas to low-carbon olefine and preparation method thereof | |
| CN104275189B (en) | Catalyst of high temperature sintering type preparation of low carbon olefines by synthetic gas and preparation method thereof | |
| CN109304216B (en) | Catalyst for producing low-carbon olefin by synthesis gas one-step method | |
| CN103521239B (en) | The Catalysts and its preparation method of F-T synthesis producing light olefins | |
| CN109304215B (en) | Catalyst for preparing low-carbon olefin by synthesis gas one-step method | |
| CN109305870B (en) | Method for preparing low-carbon olefin by synthesis gas one-step method | |
| CN109305871B (en) | Method for producing low-carbon olefin by synthesis gas one-step method | |
| CN106607052B (en) | Sulfur-bearing iron-based catalyst of high temperature sintering type and preparation method thereof | |
| CN109647492A (en) | Synthesis gas directly produces the catalyst of low-carbon alkene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |