CN1077893C - Method and apparatus for producing cyclopentadienyl manganese tricarbonyl - Google Patents
Method and apparatus for producing cyclopentadienyl manganese tricarbonyl Download PDFInfo
- Publication number
- CN1077893C CN1077893C CN97122153A CN97122153A CN1077893C CN 1077893 C CN1077893 C CN 1077893C CN 97122153 A CN97122153 A CN 97122153A CN 97122153 A CN97122153 A CN 97122153A CN 1077893 C CN1077893 C CN 1077893C
- Authority
- CN
- China
- Prior art keywords
- reactor
- pipeline
- cyclopentadiene
- turbine agitator
- diameter
- 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.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 25
- DEIHRWXJCZMTHF-UHFFFAOYSA-N [Mn].[CH]1C=CC=C1 Chemical compound [Mn].[CH]1C=CC=C1 DEIHRWXJCZMTHF-UHFFFAOYSA-N 0.000 title 1
- 238000004519 manufacturing process Methods 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 19
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012429 reaction media Substances 0.000 claims abstract description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 25
- CLLSOFHOYCGNJP-UHFFFAOYSA-N carbon monoxide cyclopenta-1,3-diene manganese Chemical compound [Mn].[C]=O.[C]=O.[C]=O.C1C=CC=C1 CLLSOFHOYCGNJP-UHFFFAOYSA-N 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- 238000005810 carbonylation reaction Methods 0.000 claims description 12
- 230000006315 carbonylation Effects 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 10
- 239000007790 solid phase Substances 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- 238000005987 sulfurization reaction Methods 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 5
- NUUNDIOOYFEMQN-UHFFFAOYSA-N cyclopenta-1,3-diene;sodium Chemical compound [Na].C1C=CC=C1 NUUNDIOOYFEMQN-UHFFFAOYSA-N 0.000 claims description 5
- 230000007246 mechanism Effects 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000009434 installation Methods 0.000 claims description 2
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 abstract description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 abstract 2
- 239000000446 fuel Substances 0.000 abstract 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 1
- 150000002902 organometallic compounds Chemical class 0.000 abstract 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 description 14
- 238000011027 product recovery Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- -1 carbonyl metal compound Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- ALKWJXWZUTYERW-UHFFFAOYSA-L O.O.O.O.[Mn](=O)(Cl)Cl Chemical class O.O.O.O.[Mn](=O)(Cl)Cl ALKWJXWZUTYERW-UHFFFAOYSA-L 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- UOSXPFXWANTMIZ-UHFFFAOYSA-N cyclopenta-1,3-diene;magnesium Chemical compound [Mg].C1C=CC=C1.C1C=CC=C1 UOSXPFXWANTMIZ-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a production method and equipment of cyclopentadienyl tricarbony manganese, in particular to a synthesis process of a metal organic compound, and the cyclopentadienyl tricarbony manganese is an anti-knock additive for engine fuel. Compared with the existing method, the production method and the equipment provided by the invention ensure high stirring efficiency of the reaction medium, reduce the synthetic reaction process to 15-20 minutes, and increase the recovery rate of the product to 95.2%.
Description
The present invention relates to a kind of production method and equipment of cyclopentadiene tricarbonyl manganese, relate to a kind of metal-organic synthesis technique specifically, promptly produce the method and the equipment thereof of cyclopentadiene tricarbonyl manganese.Cyclopentadiene tricarbonyl manganese is a kind of antiknock dope that is used for motor spirit.
As everyone knows: cyclopentadiene tricarbonyl manganese can be by the salt of the cyclopentadiene of the manganic compound of two valencys and potassium, sodium, lithium, aluminium and bromated bis-cyclopentadiene magnesium and carbon monoxide in solvent (tetrahydrofuran (THF), benzene etc.), pressure is the 190-200 normal atmosphere, and temperature 180-190 ℃ synthetic down.
At present, existing method of producing cyclopentadiene tricarbonyl manganese, the problem of bringing is: although under the situation of adjusting various parameters, product recovery rate only reaches 68%, and a production cycle need reach 15 hours.In existing production process, also can produce a large amount of asphalt tars and the byproduct that can not handle in addition.So existing production method of producing cyclopentadiene tricarbonyl manganese also exists serious deficiency.
According to existing technological achievement, more close carbonyl metal compound draws the molecular formula of following standard: RM (CO) x
R: unsaturated cyclic hydrocarbon, carbon atom are 5 to 15;
M: periodic table of elements V-VI group 4 transition metal;
X:2 to 4.
Carbonylation processes is: the unsaturated cyclic hydrocarbon of sodium or lithium is under the pressurising condition of heating and rare gas element, CO (carbon monoxide converter) gas, and in the tetrahydrofuran (THF) medium, carry out building-up reactions under 4 to the 22 kilohertz ultrasonic wave effects, its temperature is 80-170 ℃, and pressure is 30-280 normal atmosphere.
Above-mentioned technology, sodium family metal derive under compound and the endless effect of carbon monoxide (CO) periodicity, can produce a series of carbonyl metal compounds.Sodium Metal 99.5 acts on mutually with cyclopentadiene in tetrahydrofuran (THF) suspension, and the transition group carbonyl compound is being arranged: under pentacarbonyl iron Fe (CO) condition, above-mentioned reaction can take place, generate cyclopentadiene sodium suspension.
Above-mentioned technology is through after improving, though product recovery rate can reach 60-80%, the production cycle can be 1-3 hour, because the validity of its mixing effect is poor, so product recovery rate and production cycle still can not be satisfactory.
The objective of the invention is to: a kind of production method of cyclopentadiene tricarbonyl manganese is provided,, reaches high product recovery rate and shorten the production cycle to quicken carbonylation processes.
The object of the present invention is achieved like this: cyclopentadiene sodium and Manganese chloride anhydrous are in organic solvent, with carbonyl reaction condition thereafter be: under the inert atmosphere, medium is a tetrahydrofuran (THF), under heating and high pressure and stirring action, the additive that adds transition metal carbonyl compound, sulfuration dicarbapentaborane iron add-on is: 0.05-0.10%ML.Solid phase and liquid phase stirring velocity are no less than 10 meter per seconds.
Use sulfuration dicarbapentaborane iron, guaranteed the uniform distribution of reflection material, quickened carbonylation processes.If reduce sulfuration dicarbapentaborane iron add-on; If be less than 0.05%ML, process there is not influence; If surpass 0.1%ML, make reactant form the accumulation of intermediate compound (as iron and sulphur), thereby reduce product recovery rate.
The production method of cyclopentadiene tricarbonyl manganese of the present invention is characterized in that:
1. select to have the reactor of whipping appts and medium heating jacket, and in reactor, carry out,
2. with rare gas element CO reactor is carried out purge earlier, under 10 ℃ of temperature, the tetrahydrochysene furan of institute's requested number fed and sodium Metal 99.5 injection still in, reactor repeats purge with rare gas element, then, its production process is carried out in inert atmosphere,
3. subsequently reactive material is stirred, add cyclopentadiene, when stopping to decompose hydrogen, the proved response process stops, and generates cyclopentadiene sodium (CHNa),
4. at ambient temperature, add Manganous chloride tetrahydrate and sulfuration dicarbapentaborane iron 0.05-0.10%ML, stir, be heated to 60 ℃, add CO to reactor then, reactor is no less than the 80-100 normal atmosphere being full of to be forced under the CO condition, reaction medium is heated to 250-260 ℃, continually strengthen stirring velocity, the relative stirring velocity with liquid phase of the solid phase of its reaction medium is not less than 10 meter per seconds
5. carbonylation process is to finish when stopping to absorb CO, after this stops heating, and under agitation condition, stir on the limit, and the limit cooling is cooled to room temperature, and reactive material is discharging from reactor, promptly gets coarse fodder product of the present invention,
6. be to separate out under 80-95 ℃ in temperature under the vacuum distilling condition, finishing the refining of product, promptly getting the yellow crystal powder-product of cyclopentadiene tricarbonyl manganese of the present invention.
Its feature also is: its temperature of described carbonylation process is carried out under 150-260 ℃ of condition.
Its feature also is: its pressure of described carbonylation process carries out under the 80-100 atmospheric pressure.
Its feature also is: the relative stirring velocity with liquid phase of the solid phase of described its reaction medium of stirring velocity is not less than 10 meter per seconds.
The present invention compared with prior art, it has quickened carbonylation processes, has shortened the production cycle, the production cycle is 15-20 minute, has improved product recovery rate, the rate of recovery of cyclopentadiene tricarbonyl manganese is 91-93%.
Embodiment
1. select 6 liter reactors of the present invention for use, and in this still, carry out, be provided with whipping appts and medium heating jacket in the reactor.
2. with rare gas element CO reactor is carried out purge earlier, blown inert gas also adds 3.3 liters of tetrahydrofuran (THF)s, and 253 gram sodium Metal 99.5s are suspended state in the tetrahydrochysene medium.Repeat purge with rare gas element.
3. begin slow stirring (solid phase, liquid phase stirring velocity in reaction medium is 0.01 meter per second), under less than 10 ℃ of conditions of temperature, add 730 gram cyclopentadiene, when stopping to decompose hydrogen, the proved response process stops, and generates cyclopentadiene sodium (C
5H
5Na).
4. at ambient temperature, in solvents tetrahydrofurane, add 700 gram Manganous chloride tetrahydrates and 10.3 gram (0.1 mole) sulfuration dicarbapentaborane iron mixtures, stir, be heated to 60 ℃, add CO to reactor then, make it to be forced into 80 atmospheric pressures with suspended state.And temperature 250-260 ℃.Reactive material stirs.Its solid phase and liquid phase stir speed of relative movement and are not less than 10 seconds/meter.Stop through reactor internal drop in 15 minutes.The proved response material is drawn CO and is stopped, and proves that simultaneously carbonyl reaction stops.
5. lower the temperature and stop to stir, reactant is cooled to room temperature, and reactive material is discharging from reactor, promptly gets the coarse fodder product of cyclopentadiene tricarbonyl manganese of the present invention.
6. separate out in temperature 80-95 ℃ in vacuum distilling, under these processing condition, finish the refining of product, obtain 1126.2 gram cyclopentadiene tricarbonyl manganese yellow crystal powder.Its fusing point is 75-76 ℃, and product recovery rate is 93%.
At present, in order to realize the production process of cyclopentadiene tricarbonyl manganese, the production unit of its required employing also is a good problem to study, and existing this kind equipment, its structure is owing to only be fixed with turbine (turbine type) agitator on the central shaft in still, so when the turbine agitator stirs, under high-revolving rotation condition, the centre forms a doline viscous flow cone above rotating liquid, along with the rising of liquid level, it is big that periphery also becomes thereupon, promptly makes stirring velocity slow down, mixing effect is poor, and carbonyl is than the reaction times lengthening of reaction process.Current production devices does not have and can the needed high strength of realization response medium stir thus, can not ensure in the reflection medium solid phase and liquid phase are effectively mixed, and production efficiency is lower.
The present invention also aims to: a kind of equipment of producing cyclopentadiene tricarbonyl manganese is provided,, reaches high product recovery rate and shorten the production cycle to quicken carbonylation processes.
The object of the present invention is achieved like this, it is mainly by housing (1), pipeline (2-5), transmission mechanism (6), central shaft (7), turbine agitator (8), spiral stirrer (9), heating jacket parts such as (11) are formed, the outside of housing (1) is provided with heating jacket (11), housing (1) is provided with pipeline (2), pipeline (3), pipeline (4) and pipeline (5), heating jacket (11) is provided with pipeline (12) and pipeline (13), it is characterized in that being provided with in the housing (1) central shaft (7), be connected with turbine agitator (8) in the bottom of central shaft (7), also be connected with spiral stirrer (9) on the top of the middle and lower part of central shaft (7) turbine agitator (8), the top of central shaft (7) is connected with transmission mechanism (6).
Its feature is that also the described turbine agitator (8) and the diameter of spiral stirrer (9) and the relation of its installation site are:
The diameter of turbine agitator (8): the internal diameter=0.4-0.6 of reactor
The diameter of turbine agitator (8): the diameter=1.3-1.7 of spiral stirrer (9)
Height at the bottom of turbine agitator (8) and the reactor still: the diameter=0.5-0.7 of turbine agitator (8)
Height at the bottom of spiral stirrer (9) and the reactor still: the diameter=1.2-1.6 of spiral stirrer (9).
Reactor equipment of the present invention compared with prior art, it is reasonable in design, the needed high-intensity stirring of energy realization response medium, having ensured in the reflection medium effectively mixes solid phase and liquid phase, quickened the process of carbonylation reaction, reached high product recovery rate and shortened the production cycle.
Below in conjunction with drawings and Examples the utility model is further specified:
Accompanying drawing is produced the sectional structure synoptic diagram of the high pressure synthesis reactor of cyclopentadiene tricarbonyl manganese for the present invention.
Among the figure: 1, housing, 2, pipeline, 3, pipeline, 4, pipeline, 5, pipeline, 6, transmission mechanism, 7, central shaft, 8, the turbine agitator, 9, spiral stirrer, 10, expansion section, 11, heating jacket, 12, pipeline, 13, pipeline.
As can be seen from the figure: device of the present invention, that adopts is still cylindrical with process pipe Autoclave, its tumbler, rotary middle spindle and also belong to existing skill at the turbine agitator that axle is equipped with Art, device characteristic of the present invention are to stir near near the spiral that has increased vertical rib type the inner wall of kettle Device, it can make the center funnel that liquid upper forms in the above-mentioned whipping process play destruction, this In the course of reaction under the state, the formed funneling cone in the center of reaction medium is stirred by spiral and destroys , that is to say that the turbine agitator forms the horizontal circular rotating that two central shafts are the center of circle in liquid Stream circle, and spiral agitator, rib shape blade has then formed the square crossing fluid that intersects with it, each other Offset, guaranteed the turbulent flow of media fluid inner fluid. Therefore, reaction medium has obtained effectively stirring Mix, reduced the reaction time, increased production efficiency.
The mixing effect of solid phase and liquid phase is by the angle of central shaft and how much of agitator in the evaluation medium Size and deciding, if, reducing the proportionate relationship of above-mentioned physical dimension, mixing effect will reduce. This Under the state, turbine and spiral agitator are close, and only mix mutually reaction medium mixed in reactor bottom Closing effect only carries out among a small circle in the reactor bottom; If above-mentioned physical dimension proportionate relationship is also strengthened Reaction efficiency is reduced. This is instead because reaction medium is stirred that the effective coverage is improved with the turbine agitator Answer the still bottom to form the stagnant area, and spiral agitator also increase, even in turbine stirring action zone On, both circular flows of forming do not interact each other like this, form that turbulent flow stirs thereby reduced Condition.
In a word, production method provided by the present invention and equipment are compared with existing method, have guaranteed anti-Answer medium that high stirring efficiency is arranged, synthetic reaction process reduces to 15-20 minute, and product is increased to 95.2% The rate of recovery.
Claims (6)
1, a kind of production method of cyclopentadiene tricarbonyl manganese is characterized in that:
1. select to have the reactor of whipping appts and medium heating jacket, and in reactor, carry out,
2. with rare gas element CO reactor is carried out purge earlier, tetrahydrofuran (THF) and sodium Metal 99.5 with institute's requested number under 10 ℃ of temperature inject in the still, and reactor repeats purge with inert gas, and then, its production process is carried out in inert atmosphere,
3. subsequently reactive material is stirred, add cyclopentadiene, when stopping to decompose hydrogen, the proved response process stops, and generates cyclopentadiene sodium (C
5H
5Na),
4. at ambient temperature, add Manganous chloride tetrahydrate and sulfuration dicarbapentaborane iron 0.05-0.10%ML, stir, be heated to 60 ℃, add CO to reactor then, reactor is no less than the 80-100 normal atmosphere being full of to be forced under the CO condition, reaction medium is heated to 250-260 ℃, continually strengthen stirring velocity, the relative stirring velocity with liquid phase of the solid phase of its reaction medium is not less than 10 meter per seconds
5. carbonylation process is to finish when stopping to absorb CO, after this stops heating, and under agitation condition, stir on the limit, and the limit cooling is cooled to room temperature, and reactive material is discharging from reactor, promptly gets coarse fodder product of the present invention,
6. be to separate out under 80-95 ℃ in temperature under the vacuum distilling condition, finishing the refining of product, promptly getting the yellow crystal powder-product of cyclopentadiene tricarbonyl manganese of the present invention.
2, the production method of cyclopentadiene tricarbonyl manganese according to claim 1, its feature also is: its temperature of described carbonylation process is carried out under 150-260 ℃ of condition.
3, the production method of cyclopentadiene tricarbonyl manganese according to claim 1, its feature also is: its pressure of described carbonylation process carries out under the 80-100 atmospheric pressure.
4, the production method of cyclopentadiene tricarbonyl manganese according to claim 1, its feature also is: the relative stirring velocity with liquid phase of the solid phase of described its reaction medium of stirring velocity is not less than 10 meter per seconds.
5, a kind of production unit of cyclopentadiene tricarbonyl manganese, it is mainly by housing (1), pipeline (2-5), transmission mechanism (6), central shaft (7), turbine agitator (8), spiral stirrer (9), heating jacket parts such as (11) are formed, the outside of housing (1) is provided with heating jacket (11), housing (1) is provided with pipeline (2), pipeline (3), pipeline (4) and pipeline (5), heating jacket (11) is provided with pipeline (12) and pipeline (13), it is characterized in that being provided with in the housing (1) central shaft (7), be connected with turbine agitator (8) in the bottom of central shaft (7), also be connected with spiral stirrer (9) on the top of the middle and lower part of central shaft (7) turbine agitator (8), the top of central shaft (7) is connected with transmission mechanism (6).
6, the production unit of cyclopentadiene tricarbonyl manganese according to claim 5, its feature are that also the described turbine agitator (8) and the diameter of spiral stirrer (9) and the relation of its installation site are:
The diameter of turbine agitator (8): the internal diameter=0.4-0.6 of reactor
The diameter of turbine agitator (8): the diameter=1.3-1.7 of spiral stirrer (9)
Height at the bottom of turbine agitator (8) and the reactor still: the diameter=0.5-0.7 of turbine agitator (8)
Height at the bottom of spiral stirrer (9) and the reactor still: the diameter=1.2-1.6 of spiral stirrer (9).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97122153A CN1077893C (en) | 1997-11-26 | 1997-11-26 | Method and apparatus for producing cyclopentadienyl manganese tricarbonyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97122153A CN1077893C (en) | 1997-11-26 | 1997-11-26 | Method and apparatus for producing cyclopentadienyl manganese tricarbonyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1220268A CN1220268A (en) | 1999-06-23 |
| CN1077893C true CN1077893C (en) | 2002-01-16 |
Family
ID=5176713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97122153A Expired - Fee Related CN1077893C (en) | 1997-11-26 | 1997-11-26 | Method and apparatus for producing cyclopentadienyl manganese tricarbonyl |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1077893C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8852298B2 (en) * | 2006-06-29 | 2014-10-07 | Afton Chemical Corporation | Fuel composition containing iron and manganese to reduce spark plug fouling |
| US7256303B1 (en) | 2007-02-05 | 2007-08-14 | Tee Keng Lim | Method for producing alkylated cyclopentadienyl manganese tricarbonyls |
| CN103570769A (en) * | 2013-11-22 | 2014-02-12 | 辽宁石油化工大学 | Method for synthesizing methyl cyclopentadienyl manganese tricarbonyl |
| CN109608508B (en) * | 2019-01-24 | 2019-10-25 | 洋浦傲立石化有限公司 | A kind of synthetic method of 2- methyl cyclopentyl-dialkyl-tricarbon manganium |
| CN111518144A (en) * | 2020-05-26 | 2020-08-11 | 开封泓盈化工发展有限公司 | Process for extracting cyclopentadiene tricarbonyl manganese by reduced pressure distillation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU431168A1 (en) * | 1972-07-24 | 1974-06-05 | Е. А. Чернышев, А. С. Дмитриев, А. Я. Юрин, Г. М. Грандель , Е. П. Никитенко | METHOD OF PREPARING TRIORGANOSYLILCYCLOPENTADIENYLTRICARBONYLAMARGANESE |
| SU1113383A1 (en) * | 1983-02-15 | 1984-09-15 | Институт химии и химической технологии СО АН СССР | Process for preparing manganese phenylvinylidene-pi-cyclopentadienyl carbonyl |
-
1997
- 1997-11-26 CN CN97122153A patent/CN1077893C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU431168A1 (en) * | 1972-07-24 | 1974-06-05 | Е. А. Чернышев, А. С. Дмитриев, А. Я. Юрин, Г. М. Грандель , Е. П. Никитенко | METHOD OF PREPARING TRIORGANOSYLILCYCLOPENTADIENYLTRICARBONYLAMARGANESE |
| SU1113383A1 (en) * | 1983-02-15 | 1984-09-15 | Институт химии и химической технологии СО АН СССР | Process for preparing manganese phenylvinylidene-pi-cyclopentadienyl carbonyl |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1220268A (en) | 1999-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107096487A (en) | A kind of efficient three axles stirred autoclave | |
| EP1604969A1 (en) | High shear process for making metallic esters | |
| CN1077893C (en) | Method and apparatus for producing cyclopentadienyl manganese tricarbonyl | |
| CN107188802B (en) | Method for catalyzing alcohol to depolymerize 3-hydroxybutyrate by using double-acid ionic liquid | |
| CN109535424A (en) | A kind of poly- thioamide analog compound and its preparation method and application | |
| CN1100087A (en) | Process for the preparation of carboxylic acids or corresponding esters in the presence of a catalyst based on reodium and iridium | |
| CN111848500B (en) | Method for synthesizing 2-vinylpyridine | |
| CN108295796A (en) | A kind of synthesis reactor being sufficiently stirred | |
| CN1037274C (en) | Production process of petroleum bitumen oxidizing oil slurry from catalytically cracked heavy oil | |
| CN215611571U (en) | Heavy oil continuous modification equipment for fertilizer coating agent production | |
| CN106824292B (en) | A kind of preparation method for dimethyl carbonate and the catalyst of phenylacetate diphenyl carbonate synthesis | |
| RU2128182C1 (en) | Method and apparatus for producing cyclopentadienylmagnesium tricarbonyl | |
| CN111517949B (en) | Method for synthesizing ethylene glycol phenyl ether methacrylate | |
| CN208115525U (en) | A kind of carbonaceous mesophase spherules dissolving tank | |
| CN1091074C (en) | Sodium bicarbonate preparation by catalytic circulation process and multi-phase reactor thereof | |
| CN86103852A (en) | The reactor of carrying out polymerization reactions in systems with high concentration of polymer | |
| CN1021462C (en) | Agitator for atomosphere reforming in continuous heat-treating furnace | |
| CN1062502C (en) | Apparatus and method for preparing alkali metal suspension and organic alkali metal compound solution | |
| CN218803231U (en) | Premixing device is used in plasticizer production | |
| CN217248106U (en) | Slurry stirring device | |
| CN207158836U (en) | A kind of coal chemical industrial waste water agitating device | |
| CN113413860B (en) | Solid-liquid mixing reaction kettle for preparing surfactant | |
| CN216063222U (en) | Triglycidyl isocyanurate synthesis reaction equipment | |
| CN218945054U (en) | A reation kettle for polyester resin preparation's high mixing rate | |
| CN215396187U (en) | Stirring device for polyethylene wax cold mixing compounding |
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 | ||
| C57 | Notification of unclear or unknown address | ||
| DD01 | Delivery of document by public notice |
Addressee: Liang Xiufeng Document name: Reply to a patent inquiry |
|
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CI01 | Publication of corrected invention patent application |
Correction item: Termination of patent right Correct: delete False: Termination of patent right Number: 4 Volume: 21 |
|
| ERR | Gazette correction |
Free format text: CORRECT: CESSATION OF PATENT RIGHT; FROM: CESSATION OF PATENT RIGHT TO: DELETION |
|
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |