CN208340685U - Fluidized bed reaction - Google Patents
Fluidized bed reaction Download PDFInfo
- Publication number
- CN208340685U CN208340685U CN201820524374.7U CN201820524374U CN208340685U CN 208340685 U CN208340685 U CN 208340685U CN 201820524374 U CN201820524374 U CN 201820524374U CN 208340685 U CN208340685 U CN 208340685U
- Authority
- CN
- China
- Prior art keywords
- reactor
- height
- catalyst
- sectional area
- fluidized bed
- 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.)
- Withdrawn - After Issue
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/0055—Separating solid material from the gas/liquid stream using cyclones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1836—Heating and cooling the reactor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
[project] is provided in fluidized-bed reaction, the contacting efficiency of catalyst and raw material increases and catalyst disperses reduction and the raised fluidized bed reaction of space time yield.[solution] fluidized bed reaction, it has reactor, with the inner space for storing flowable catalyst, using the height of the lowest point of inner space as benchmark, the average height of the inlet portion lower end of cyclone separator is set as h, the internal diameter of reactor at height h is set as upper inner diameter D1, when the mean inside diameter of reactor at the height h ' of h/2~h/4 is set as lower inner diameter D2, D1/D2 is more than 1.000 and is 1.310 or less, effective sectional area at height h is set as top effective sectional area A1, when average effective sectional area at height h ' is set as lower part effective sectional area A2, A1/A2 is more than 1.18 and is 1.88 or less.
Description
Technical field
The utility model relates to fluidized bed reactions.
Background technique
The ammoxidation reaction of fluidized-bed reactor has been used industrially to implement since ancient times.In order to improve α, β-unsaturation
The reaction yield of nitrile, as the exploitation of catalyst and the improvement of inside reactor device, such as carried out unstrpped gas dispersion pipe,
The improvement of dispersion plate.In whip rock, gloomy taste victory, just tough " the reaction engineering (the anti-ying engineering of fluidized bed) of fluidized bed " (times wind of hole tail
Shop (1984) distribution), Fluidization Engineering (fluidized bed engineering)；DAIZO KUNII·OCTAVE
Extremely general fluidized-bed reaction technology is carried out in LEVENSPIEL (JOHNWILEY&SONS.INC, (1969) distribution)
Explanation.
In plant-scale device, due to continuously carrying out production operating for a long time, generation impacts reaction yield
Catalyst activity reduce and catalyst outflow caused by catalyst loading reduction, catalyst particle size distribution change
Change etc..Therefore, in continuously running, the adjustment of these catalyst activity loading particle diameter distributions etc. is usually carried out.Such as with
Reaction yield is maintained as a purpose, in order to supplement the amount of the catalyst to disperse to outside fluidized-bed reactor, prevent in catalyst
The concentration of active constituent reduces and newly catalysis is given back or exchanged to additional catalyst or a part of catalyst of taking-up after being regenerated
The total amount of agent.In addition, for the recovery processing of the catalyst requirement to outside reactor of dispersing.
As many and diverse, facility load the technology for solving aforesaid operations, it is anti-that a kind of flowing is disclosed in patent document 1
Induction method and apparatus for carrying out this method, the flowing reactive method be characterized in that, for using fluidized-bed reactor into
The method of row flowing reactive in this method, a part of the granular catalyst in fluidized-bed reactor is taken out, takes out the institute
Catalyst be classified to obtain fine particle size catalyst, which is returned to same in aforementioned fluidized-bed reactor
When, not used granular catalyst is supplemented, and adjust fine particle size catalytic amount ratio shared in whole granular catalysts.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2005-193172 bulletin
Utility model content
Utility model will solve the problems, such as
Improve reactor by supplementing unused catalyst as a small amount of as possible according to the technology recorded in patent document 1
The mobility of interior catalyst, it is possible thereby to the production efficiency of high acrylonitrile is maintained for a long time, but dispersing with catalyst
The taking-up and the operation of supplement itself for carrying out catalyst necessitate.That is, the technology recorded in patent document 1 is not used to prevent
The solution for the essence that only catalyst disperses.In turn, from the viewpoint of raising α, the production efficiency of alpha, beta-unsaturated nitriles, specially
The technology recorded in sharp document 1 remains on that there are rooms for improvement.
The utility model is proposed in view of the problems of above-mentioned prior art, is being flowed it is intended that providing
Change in bed reaction, the fluidized bed that the contacting efficiency of catalyst and raw material is high and catalyst disperses reduces and space time yield is high is anti-
Answer the manufacturing method of device and 'alpha ', ' bela '-unsaturated nitrile.
The solution to the problem
The inventors of the present invention's further investigation, as a result, it has been found that, by adjusting the structure of the upper and lower part of fluidized bed reaction,
It can solve problem, so as to complete the utility model.
That is, the utility model is as described below.
[1] a kind of fluidized bed reaction, which is characterized in that it has reactor, and the reactor has storage can
The inner space of the catalyst of flowing, and aforementioned inner space have for autoreaction gas removal heat cooling coil,
With for autoreaction gas separation and recovery aforementioned catalytic agent cyclone separator,
Using the height of the lowest point of aforementioned inner space as benchmark, by the flat of the inlet portion lower end of aforementioned cyclone separator
The internal diameter for being highly set as the previous reaction device at h, height h is set as aforementioned at upper inner diameter D1, h/2~h/4 height h '
When the mean inside diameter of reactor is set as lower inner diameter D2, D1/D2 be more than 1.000 and for 1.310 hereinafter,
Effective sectional area at aforementioned height h is set as the average effective at top effective sectional area A1, aforementioned height h ' and cuts
When area is set as lower part effective sectional area A2, A1/A2 is more than 1.18 and is 1.88 or less.
[2] fluidized bed reaction according to [1], which is characterized in that previous reaction device is also equipped with to aforementioned inner
Space imports multiple unstrpped gas dispersers of unstrpped gas,
The lowest point in aforementioned inner space is to be configured on the nozzle upper surface of the unstrpped gas disperser of extreme lower position
Point.
[3] fluidized bed reaction according to [1] or [2], which is characterized in that aforementioned lower inner diameter D2 be 3m~
10m。
[4] fluidized bed reaction according to any one of [1]~[3], which is characterized in that aforementioned lower part is effectively cut
Area A2 is 6m2~70m2。
[5] fluidized bed reaction according to any one of [1]~[4], which is characterized in that aforementioned cyclone separator
Inlet portion lower end average height h be 10m~25m.
[6] fluidized bed reaction according to any one of [1]~[5], which is characterized in that previous reaction device is certainly
At least part in the region of aforementioned height h to h ' have by internal diameter decrescence in a manner of the part that is constituted,
It is 25 °~40 ° that the inner wall and plumb line of preceding sections, which are formed by angle Θ,.
The effect of utility model
It according to the utility model, provides in fluidized-bed reaction, the contacting efficiency of catalyst and reaction raw materials is increased and urged
Agent disperse reduction and space time yield raised fluidized bed reaction and 'alpha ', ' bela '-unsaturated nitrile manufacturing method.
Detailed description of the invention
Fig. 1 is to exemplify the schematic sectional view of the fluidized bed reaction of a mode of present embodiment.
Fig. 2 is the schematic sectional view of fluidized bed reaction used in embodiment 1.
Fig. 3 is the schematic sectional view of fluidized bed reaction used in embodiment 2.
Fig. 4 is the schematic sectional view of fluidized bed reaction used in embodiment 3.
Fig. 5 is the schematic sectional view of fluidized bed reaction used in comparative example 1~2.
Fig. 6 is the schematic sectional view of fluidized bed reaction used in comparative example 3~4.
Fig. 7 is the schematic sectional view of fluidized bed reaction used in comparative example 5~6.
Description of symbols
1 fluidized bed reaction
2 reactors
3 air (oxygen) ingress pipe
4 air (oxygen) dispersion plate
5 raw material ingress pipes
6 stock dispersion pipes
7A cooling coil
7B cooling coil
7C cooling coil
8A cyclone separator
8B cyclone separator
8C cyclone separator
9 cyclone inlets
10A dipping tube
10B dipping tube
10C dipping tube
Specific embodiment
For mode (hereinafter referred merely to as " this for implementing the utility model while below according to need with reference to the accompanying drawings
Embodiment ") it is described in detail.Present embodiment below is the illustration for illustrating the utility model, and objective not will
The utility model is defined in the following contents.The utility model can be deformed within the scope of its subject matter to implement.It needs
It is bright, in attached drawing, same appended drawing reference is added for same element, repeat description is omitted.In addition, waiting positions up and down
Relationship, unless otherwise specified, then positional relationship based on the figure.In turn, the dimensional ratios of attached drawing are not limited to illustrate
Ratio.
The fluidized bed reaction of present embodiment has reactor, and the reactor, which has, stores flowable catalysis
The inner space of agent, and have in aforementioned inner space for the cooling coil of autoreaction gas removal heat and for reflexive
The cyclone separator for answering gas separation and recovery aforementioned catalytic agent will using the height of the lowest point of aforementioned inner space as benchmark
The internal diameter that the average height of the inlet portion lower end of aforementioned cyclone separator is set as the previous reaction device at h, height h is set as in top
When the mean inside diameter of previous reaction device at diameter D1, h/2~h/4 height h ' is set as lower inner diameter D2, D1/D2 is more than 1.000
And for 1.310 hereinafter, the effective sectional area at aforementioned height h is set as being averaged at top effective sectional area A1, aforementioned height h '
When effective sectional area is set as lower part effective sectional area A2, A1/A2 is more than 1.18 and is 1.88 or less.Due to so constituting, this reality
The fluidized bed reaction for applying mode, which in fluidized-bed reaction, can increase the contacting efficiency of catalyst and raw material and reduce, urges
Agent disperses and increases space time yield.
The fluidized bed reaction of one mode of present embodiment is illustrated in Fig. 1.
Reactor 2 in fluidized bed reaction 1 is equivalent to the reaction system for dividing fluidized-bed reaction and external gas phase
The main part of reaction unit is not particularly limited as its shape, can be applicable in various known shapes.
Reactor 2 can be formed in the structure that its inner space for example has following equipment:
Connect with the bottom of the reactor 2, into reaction system import air (oxygen) air (oxygen) ingress pipe 3；
It is set to the lower part of 2 inner space of reactor, disperses the air (oxygen) as raw material in reaction system
Air (oxygen) dispersion plate 4；
The original for connecting, importeding into the raw material other than air (oxygen) in reaction system with aftermentioned 6 top of stock dispersion pipe
Expect ingress pipe 5；
It is set to the lower part of 2 inner space of reactor, reaction heat is controlled to temperature (the reaction temperature of inner space except heat
Degree) cooling coil 7A, 7B and 7C；
The lower part for being set to 2 inner space of reactor, the stock dispersion pipe 6 for dispersing raw material in reaction system；
The catalyst layer (not shown) that fluid catalyst by being filled in 4 top of air (oxygen) dispersion plate is constituted；
It is configured at cyclone separator 8A, 8B and the 8C on the top of 2 inner space of reactor；
It is equivalent to the cyclone inlet 9 of the entrance of cyclone separator 8A；With
Dipping tube 10A, 10B and the 10C being connect with the cyclone separator 8A, 8B and 8C.
In Fig. 1, using the height of the lowest point of the inner space of reactor 2 as benchmark, as line segment X-X ' and line segment Y-
H shown in the distance of Y ' indicates the average height of the inlet portion lower end of aforementioned cyclone separator.That is, in Fig. 1, shown in line segment Y-Y '
Position correspond to position shown in the height (0m) of lowest point of inner space, line segment X-X ' and correspond to entering for cyclone separator
The average height (hm) of oral area lower end.
" average height " of the inlet portion lower end of cyclone separator refers to that there are the feelings of multiple series in cyclone separator
Under condition, the height of the lower end of multiple cyclone inlets 9 is calculated with average value.In mode illustrated by Fig. 1, whirlwind
Separator is only three series being connected in series, therefore the whirlwind from the position of line segment Y-Y ' to height for reactor direction divides
The average height of position from device entrance 9 as the inlet portion lower end of cyclone separator.
It should be noted that unstrpped gas disperser refers to 4 He of air (oxygen) dispersion plate in mode illustrated by Fig. 1
Both stock dispersion pipes 6.The lowest point of the inner space of reactor 2, for the unstrpped gas disperser for being configured at extreme lower position
Nozzle or opening portion (hereinafter referred merely to as " nozzle ") upper surface, i.e. air (oxygen) dispersion plate 4 on point.In this way, in this implementation
In mode, from the viewpoint of reaction efficiency, preferred reactor is also equipped with to aforementioned inner space and imports the multiple of unstrpped gas
Unstrpped gas disperser, aforementioned inner space lowest point be table on the nozzle for be configured at the unstrpped gas disperser of extreme lower position
Point on face.At this point, catalyst is present in top compared with the nozzle upper surface of the unstrpped gas disperser.
The lowest point of inner space in present embodiment is not limited to above-mentioned, such as the nozzle phase with unstrpped gas disperser
Than lower part can be located at.
In present embodiment, the average height h of the inlet portion lower end of cyclone separator is not particularly limited, but it is excellent
It is selected as 10m~25m, more preferable 12m~20m.
In present embodiment, the internal diameter of the reactor 2 at average height h is set as upper inner diameter D1, h/2~h/4 height
When the mean inside diameter of reactor 2 at h ' is set as lower inner diameter D2, D1/D2 is more than 1.000 and is 1.310 or less.It is illustrated in Fig. 1
Mode in, corresponding to line segment X-X ' position internal diameter be upper inner diameter D1.The lower inner diameter D2 of reactor 2 can be used as pair
Should the average value of internal diameter of the internal diameter in the position of h/2 and the position corresponding to h/4 find out.
D1/D2 is in 1.000 situations below, and the gas linear velocity (LV) of catalyst layer increases, and mobility improves, still
Due to LV raising, the space density of the catalyst at reactor top is increased, and is increased to the load of cyclone separator, catalyst
It disperses increase.It is preventing on catalyst from dispersing, it is contemplated that reduce LV.Here, the LV adjustment of reactor can usually pass through reaction
The pressure of device is adjusted, and increases pressure to reduce LV.Adjoint reaction is increased as a result, existing and generating reaction pressure
The tendency that achievement reduces.
On the other hand, be more than 1.000 by D1/D2, can in the state of keeping the LV of high catalyst layer, it is i.e. not sacrificial
Domestic animal reduces the space density of the catalyst at reactor top in the case where reacting achievement, can take into account mobility improves and be catalyzed
Agent, which is dispersed, to be prevented.
In addition, in the case that D1/D2 is more than 1.310, there are the tendencies that space time yield reduces, therefore from space (space)
From the viewpoint of efficiency improves (machine energy consumption reduction), D1/D2 is set as 1.310 or less.
Consider that D1/D2 is preferably 1.030~1.200, more preferable 1.050~1.150 from above-mentioned viewpoint.
D1/D2 can for example be measured by the method recorded in aftermentioned embodiment.
In present embodiment, upper inner diameter D1 is not particularly limited, it is preferred that being 3.1m~12.0m, more preferable
5.3m~11.5m.In addition, lower inner diameter D2 is not particularly limited, it is preferred that for 3m~10m, more preferable 5.0m~
10.0m。
In present embodiment, the effective sectional area at average height h is set as flat at top effective sectional area A1, height h '
When equal effective sectional area is set as lower part effective sectional area A2, A1/A2 is more than 1.18 and is 1.88 or less.
It should be noted that effective sectional area refers in other than interposer part in fluidized-bed reactor etc.
Tolerant (i.e. catalyst) actually flowable sectional area.
That is, considering from above-mentioned viewpoint, it is contemplated that the catalyst in fluidized-bed reactor for the range from height h to h '
Actually flowable region, A1/A2 are more than 1.18 and are 1.88 or less.From the same viewpoint, A1/A2 is preferably
1.25~1.65, more preferable 1.35~1.50.
A1/A2 can for example be measured by the method recorded in aftermentioned embodiment.
In present embodiment, top effective sectional area A1 is not particularly limited, it is preferred that being 7m2~115m2, more
It is preferred that 20m2~98m2.In addition, lower part effective sectional area A2 is not particularly limited, it is preferred that being 6m2~70m2, it is more excellent
Select 15m2~63m2。
In present embodiment, from the viewpoint of further increasing mobility while preventing catalyst buildup, preferably instead
Answer device at least part in the region from aforementioned height h to h ' have by internal diameter decrescence in a manner of the part that is constituted (below
Referred to as coupling part), to be formed by angle Θ be 25 °~40 ° for the inner wall of the part and plumb line.It is examined from same viewpoint
Consider, angle Θ is more preferably 25 °~30 °.
In present embodiment, deposited in the lower part of above-mentioned coupling part there are reactor lower part, on the top of coupling part
On reactor top.Preferred reactor lower part and reactor top are respectively provided with approximately fixed the region A and B of internal diameter.It is substantially solid
Surely the change rate for referring to the internal diameter from the lowest part in the region until topmost is 1% or less.
Here, using the height of the lowest point of inner space as benchmark (0m), above-mentioned coupling part is preferably placed at 5~15m
Between, be more preferably located between 8~12m.
The α of present embodiment, the manufacturing method of alpha, beta-unsaturated nitriles use the fluidized bed reaction of present embodiment, preferably
Include to the inner space of the fluidized bed reaction import ammonia, oxygen-containing gas and selected from by propylene, propane, isobutene and
At least one of the group of tert-butyl alcohol composition substance, the process reacted in the presence of aforementioned catalytic agent, aforementioned catalytic agent
Contain molybdenum.
That is, the fluidized-bed reaction in present embodiment, by ammonia, oxygen-containing gas and selected from propylene, propane, isobutene and
At least one of tert-butyl alcohol substance (hereinafter also referred to hydrocarbon or the tertiary alcohol) is supplied to reactor lower part simultaneously with gas phase, and manufacture institute is right
The 'alpha ', ' bela '-unsaturated nitrile answered.
Fluidized-bed reaction specifically may include: to the fluidized-bed reactor base feed gas comprising catalyst layer,
The process for flowing catalyst layer；Unstrpped gas is set to obtain the process that reaction generates gas by catalyst layer；Gas will be generated
Body self-catalysis oxidant layer be discharged and after importeding into cyclone separator, process that reaction is generated into gas gravity flow fluidized bed reactor discharge；
It is returned to catalyst recycling adjoint when reaction generation gas is directed to cyclone separator, by the catalyst from dipping tube
The process of catalyst layer.
It as the oxygen-containing gas for being supplied to reactor, is not particularly limited, such as air can be enumerated, containing aerobic non-live
Property gas etc., usually using air.The supply amount of oxygen-containing gas is relative to hydrocarbon or the tertiary alcohol, preferably 5~15 molar ratios, further
It is preferred that 7~14 molar ratios.The supply amount of ammonia relative to hydrocarbon or the tertiary alcohol, can preferably with 0.5~2 molar ratio, it is further preferred 1~
The range of 1.5 molar ratios uses.
Temperature in catalyst layer is preferably 300~600 DEG C, 400~500 DEG C further preferred, and pressure is preferably
3Kg/cm2- G or less, further preferred 0.2~1.5Kg/cm2It is carried out under conditions of-G.For fluid catalyst, can be used
The palace of the Qing Dynasty rich equal " acrylonitrile (ア Network リ ロ ニ ト リ Le) " (chemical engineering, No. vol.48,11,873-881 pages (1984)), Japan are special
The supported catalyst containing molybdenum described in many documents such as clear 51-40391 bulletin, patent is opened, such as molybdenum-can be enumerated
Bismuth-Fe-series catalyst.
During carrying out fluidized-bed reaction in present embodiment, in reactor lower part, there are catalyst concentration layers, in reactor
There are catalyst dilution layers on top.That is, there is top when fluid catalyst forms flow regime in reactor and then urge
The smaller tendency of the space density of agent.Such as big hiding " liquidation method (liquidation method) " (Nikkan Kogyo Shimbun (1962) of state's well
Distribution) described in like that, in gas system, fluidized bed height may not as liquid level prescribed specific, due to the blistering of size
Foam and exist and protrude, therefore be approximate fifty-fifty specific always.
In present embodiment, the upper and lower limits of catalyst concentration layer can be used can self installation in the pressure of reactor
Nozzle measure pressure difference, using the catalyst layer height calculated by following formula as the upper limit, lower limit as the setting of air (oxygen) dispersion plate
Position and it is specific.
Catalyst layer height Lr=(pressure difference between b-h)/((pressure difference between b-c)/(distance between b-c))+(between a-b
Distance)
Here, the centre that a is the setting height of air (oxygen) dispersion plate, b is air (oxygen) dispersion plate and stock dispersion pipe
The height for the top 1m that the height of point, c are b, h are cyclone inlet height.
In reactor inner space, compared with the catalyst concentration layer, density of catalyst in the fluid on top is smaller,
Referred to as catalyst dilution layer.In reactor, catalyst dilution layer region has wider usually compared with catalyst concentration layer region
Region.Reaction generates the adjoint catalyst of gas and is flowed into the cyclone separator for being set to reactor top.Adjoint urges
The most of autoreaction here of agent generates gas separation, using the dipping tube for being installed on the cyclone separator, is returned to anti-
Answer the lower part of device inner space.Although not showing in Fig. 1 it should be noted that the reaction of self-catalysis agent separation generates gas
Out, it but can be exported to outside reactor by the delivery line for being installed on cyclone separator top.In addition, in Fig. 1, cyclone separator
It depicts only 1 series (3), but cyclone separator number generates gas according to the size of reactor, catalyst particle size and reaction
The scale of construction determines, is usually arranged multiple.In addition, cyclone separator is if being set as more than two series connection, there are the trappings of catalyst
The raised tendency of efficiency.
In present embodiment, from the viewpoint of reaction efficiency, at the average height h of the inlet portion lower end of cyclone separator
, carry out fluidized-bed reaction during, the space density of the aforementioned catalytic agent that is present in aforementioned inner space (i.e., be present in unit
The quality of the catalyst in the space of volume) it is preferably 24kg/m3Above and 73kg/m3Below, more preferably 30kg/m3~60kg/
m3。
The space density of catalyst can for example be measured by the method recorded in aftermentioned embodiment.
In catalyst concentration layer, the ammoxidation reaction of most base feed gas is carried out, generates reaction heat.The catalysis
For agent enriched layer since catalyst exists with high density, heat exchanger effectiveness is good.Equipment in order to mitigate control reaction temperature
Burden, carry out interior dress cooling coil in temperature controlled catalyst concentration layer reaction heat can be effectively removed.It is preferred that with
The mode that 40% or more of the heat transfer area of the cooling coil is present in catalyst concentration layer is arranged.In order to reduce reaction temperature
Part it is unbalanced, cooling coil can be by multiple serial groups independent with the various heat transfer areas of size
It constitutes.
Cooling coil in present embodiment can be applicable between the various known forms being set in fluidized-bed reactor
Heat exchanger is connect, its type, size and shape are not limited.The cryogen to circulate in cooling coil is that ammoxidation is anti-
The fluid of temperature or less, preferably 100~300 DEG C is answered, such as uses warm water, high pressure warm water, steam, mixture above-mentioned or melting
Salt.
[embodiment]
It is described in more detail sequentially for present embodiment by embodiment and comparative example.But present embodiment is only
Its purport is not departed from not limited by following embodiments then.
(average height h, upper inner diameter D1, lower inner diameter D2, top effective sectional area A1 and lower part effective sectional area A2)
For reactor substantially cylindric shown in Fig. 2~7, as described below, calculate average height h, upper inner diameter D1,
Lower inner diameter D2, top effective sectional area A1 and lower part effective sectional area A2.
Using the height of the lowest point of reactor inner space as benchmark, the mean height of the inlet portion lower end of cyclone separator
The internal diameter that degree is set as the previous reaction device at h, height h is set as the previous reaction at upper inner diameter D1, h/2~h/4 height h '
The mean inside diameter of device is set as lower inner diameter D2.It should be noted that the mean inside diameter of reactor is as the position corresponding to h/2
The average value of internal diameter and the internal diameter of the position corresponding to h/4 is found out.
Each height of above-mentioned h, h/2 and h/4 are located, and the cross sectional shape of reactor is all circle, therefore the sectional area at height h
It is calculated by D1, in addition, the sectional area at height h ' is calculated by D2.
Effective sectional area at aforementioned height h is had as top effective sectional area A1, by being averaged at aforementioned height h '
Sectional area is imitated as lower part effective sectional area A2, is based on following calculating.
A1=(D1/2)2×π-A1’
A1 ': (inside does not have for piping at sectional area total+height h of cyclone separator or dipping tube at height h etc.
Have the object of catalyst) sectional area amount to
A2=(D2/2)2×π-A2’
A2 ': the cooling coil sectional area at sectional area total+height h ' of cyclone separator or dipping tube at height h '
Other pipings at total+height h ' etc. are (for the content other than cyclone separator, dipping tube, cooling coil and in inside
There is no the objects of catalyst) sectional area amount to
(here, the sectional area at height h ' refers to the flat of the sectional area at sectional area and height h/4 at height h/2
Mean value.)
(the catalyst amount of dispersing)
Every 1 hour reduction amount of the catalyst amount of dispersing as the catalytic amount being calculated using following formula.
Catalytic amount W is indicated using following formula.
W=Dr × Lr × A2
Lr is indicated for catalyst layer height, using following formula.
Lr=(pressure difference between b-h)/((pressure difference between b-c)/(distance between b-c))+(distance between a-b)
(in above-mentioned formula, a is the setting height of air (oxygen) dispersion plate, b is air (oxygen) dispersion plate and stock dispersion pipe
The height for the top 1m that the height of intermediate point, c are b, h are cyclone inlet height.)
Dr is catalyst layer apparent density [kg/m3], indicated using following formula.
Dr=(pressure difference between b-c)/(distance between b-c)
(in above-mentioned formula, described in a, b and c text as defined above)
(output)
Acrylonitrile process amount is found out using following formula.
Acrylonitrile process amount (T/D)=propylene (Py) feeding coal (Nm3/ h (hour)) * acrylonitrile yield (mole %)/
100/22.4*53.06*24/1000
The quantitative analysis of acrylonitrile, unreacting propylene is carried out using device below and condition by gas chromatography.
For gas chromatography, as device, using Shimadzu GC-17A, chromatographic column using TC-FFAP 60m ×
0.32 0.25 μm of film thickness.
Detector uses helium using FID, carrier gas.
Chromatogram column temperature condition is as described below.
Initial temperature: 50 DEG C
Heating rate: 5 DEG C/min
1:180 DEG C of 15 minutes HOLD (holding) of final temperature
Heating rate: 10 DEG C/min
2:230 DEG C of 10 minutes HOLD of final temperature
3:50 DEG C of 5 minutes HOLD of final temperature
(contacting efficiency)
Contacting efficiency is found out using following formula.
Catalysis under contacting efficiency (η)=- LN (yield/100 unreacted Py) × 3.6/ time of contact (s)/reaction temperature
Agent activity (1/hr (hour)) × 100
Unreacted Py yield (%)=(molal quantity of responseless propylene)/(molal quantity of the propylene supplied) ×
100
Time of contact=catalytic amount W/ (enriched layer LV × A2* catalyst bulk density)
Enriched layer LV=F × (273.2+T) × 1.033/ (273.2 × (1.033+P) × 3600*A2)
F: always it is fed gas flow (Nm3/h)
The mean temperature (DEG C) of previous reaction device at the height h ' of T:h/2~h/4
P:Reactor TOP pressure (reactor roof pressure) (kg/cm2G)
Catalyst bulk density (kg/L): the weight (kg) in 1L container when catalyst filling
In addition, catalyst activity K at 440 DEG C utilizes following formula to calculate.
K (* 10^3/hr)=3.6*LN (100/ (100-Py conversion ratio))/time of contact (s)
Py conversion ratio is measured using following methods.
The catalyst of 1.0g is filled into the fixed-bed type reaction tube of internal diameter 10mm, is set in T=440 DEG C of reaction temperature,
With flow F=40 (Ncc/ minutes) circulation propylene: ammonia: oxygen: water: the mixing of helium=1:1.2:1.89:1.85:12.6 molar ratio
Gas.At this point, pressure P is 0MPa according to gauge pressure.
Time of contact passes through 0.60 (second) (=W/F × 60 × 273/ (273+T) × ((P+0.101)/0.101)) (gs/
Ml it) calculates.
The analysis of reaction gas is carried out by online gas chromatography.
(space density (diluent zone density of catalyst) of the catalyst in diluent zone)
By pressure difference the LR ' [kg/m of the height h and h-5 [m] in aforementioned inner space2] calculated by following formula.
Diluent zone density of catalyst [kg/m3]=LR ' [kg/m2]/5[m]
(space time yield)
Space time yield [T/Dm3] found out as the output of reactor unit void tower volume.So-called volume is made herein
It is found out to ignore the volume (the also reactor volume including the volume of internal structure object) of the internal structure object of reactor.
I.e., it is contemplated that the sectional area and height for reactor of reactor top and lower part are calculated using conventional method.
For fluidized bed reaction used in Examples 1 to 3 below and comparative example 1~6, as described later, in addition to
The value of D1, D2, A1, A2, h have differences except with it is same shown in Fig. 1.
That is, there is dispersion pipe and dispersion plate as the gas of reaction raw materials using the lower part in reactor, in addition, fluidizing
The lower part of the inner space of bed reactor configures cooling coil, and the top configuration trapping in the inner space of fluidized-bed reactor is mixed
The cyclone separator for entering the catalyst of the generation gas flowed out to autoreactor, is returned to lower part for catalyst using dipping tube
Mode is constituted.In addition, cyclone separator formed it is shown in FIG. 1 with 3 sections of cyclone separators being formed by connecting of connecting, same whirlwind
Separator configuration amounts to 8 series.Metrical instrument, auxiliary device are usually used substance, are in common error range
Substance.
[embodiment 1]
Propylene, ammonia and air, which are supplied to, becomes Mo filled with group12Bi0.20Ce0.40Fe2.0Ni5.6Mg2.2K0.07Cs0.04Institute
The oxide carried catalyst made of the silica of 50 weight % shown is (according to Japan Patent 3214984 embodiments 1
Record manufacture catalyst) upper inner diameter 9m, lower inner diameter 8m (D1/D2=1.125, A1/A2=1.40, top under
It is 30 ° that the inner wall of coupling part between portion and plumb line, which are formed by angle), length 20m, the lowest point from inner space it is straight
The fluidized-bed reactor 1-1 of the vertical cylinder type of height 10m until interconnecting piece lower end is with reactor upper gas speed
The mode of 0.57m/s (lower gas speed 0.80m/s), the ammoxidation reaction as described below for carrying out propylene.Fluidized-bed reactor
1-1 has unstrpped gas dispersion pipe, dispersion plate, except heat pipe and cyclone separator inside it.As a result, being calculated using preceding formulae
Contacting efficiency (η) out be 70%, the catalyst amount of dispersing be 1.5kg/h, the space density of catalyst in reactor top it is (dilute
Release a layer density of catalyst) it is 47kg/m3.In addition, confirmation is internal when reactor stops, the as a result connection between top and lower part
Accumulation of the part without apparent catalyst.
[embodiment 2]
Propylene, ammonia and air are supplied to upper inner diameter 8.7m, lower inner diameter 8m (D1/D2=1.088, A1/A2=
1.39, it is 30 ° that the inner wall Yu plumb line of the coupling part between top and lower part, which are formed by angle), the vertical circle of length 20m
The fluidized-bed reactor 1-2 of cartridge type is the side of 0.57m/s (lower gas speed 0.80m/s) with reactor upper gas speed
Formula, the ammoxidation reaction as described below for carrying out propylene.Structure of reactor other than reactor inside diameter is item same as Example 1
Part.As a result, it is 1.5kg/h, on reactor that the contacting efficiency (η) calculated using preceding formulae, which is 70%, the catalyst amount of dispersing,
The space density of catalyst in portion is 47kg/m3.In addition, confirmation is internal when reactor stops, as a result top and lower part it
Between coupling part there is no the accumulation of apparent catalyst.
[embodiment 3]
By propylene, ammonia and air be supplied to upper inner diameter 9m, lower inner diameter 8m (D1/D2=1.125, A1/A2=1.40,
It is 60 ° that the inner wall of coupling part between top and lower part and plumb line, which are formed by angle), the vertical cylinder type of length 20m
Fluidized-bed reactor 1-3, in such a way that reactor top superficial linear velocity in a column is 0.57m/s (lower part superficial linear velocity in a column 0.80m/s), such as
Under it is described carry out propylene ammoxidation reaction.Fluidized-bed reactor 1-3 have inside it unstrpped gas dispersion pipe, dispersion plate,
Except heat pipe and cyclone separator.As a result, the contacting efficiency (η) calculated using preceding formulae is that 70%, the catalyst amount of dispersing is
1.5kg/h, catalyst in reactor top space density be 49kg/m3.In addition, confirmation is internal when reactor stops, knot
Coupling part of the fruit between top and lower part confirmed the accumulation of the catalyst inactivated.
[comparative example 1]
By propylene, ammonia and air be supplied to upper inner diameter 8m, lower inner diameter 8m (D1/D2=1.000, A1/A2=1.10),
The fluidized-bed reactor 1-4 of the vertical cylinder type of length 20m is 0.57m/s (lower part void tower speed with reactor upper gas speed
Spend 0.63m/s) mode, the as described below ammoxidation reaction for carrying out propylene.Structure of reactor other than reactor inside diameter be with
The identical condition of embodiment 1.As a result, the contacting efficiency (η) calculated using preceding formulae is that 55%, the catalyst amount of dispersing is
1.5kg/h, catalyst in reactor top space density be 47kg/m3.In addition, confirmation is internal when reactor stops, knot
Fruit does not have the accumulation of apparent catalyst in reactor wall.
[comparative example 2]
By propylene, ammonia and air be supplied to upper inner diameter 8m, lower inner diameter 8m (D1/D2=1.000, A1/A2=1.10),
The fluidized-bed reactor 1-4 of the vertical cylinder type of length 20m is 0.73m/s (lower part void tower speed with reactor top superficial linear velocity in a column
Spend 0.80m/s) mode, the as described below ammoxidation reaction for carrying out propylene.Structure of reactor other than reactor inside diameter be with
The identical condition of embodiment 1.As a result, the contacting efficiency (η) calculated using preceding formulae is that 70%, the catalyst amount of dispersing is
2.5kg/h, catalyst in reactor top space density be 103kg/m3.In addition, confirmation is internal when reactor stops, knot
Fruit does not have the accumulation of apparent catalyst in reactor wall.
[comparative example 3]
Propylene, ammonia and air are supplied to upper inner diameter 10.5m, lower inner diameter 8m (D1/D2=1.313, A1/A2=
1.88), the inner wall with plumb line of the coupling part between top and lower part be formed by angle be 30 °), length 20m it is vertical
The fluidized-bed reactor 1-5 of cylinder type is 0.43m/s's (lower part superficial linear velocity in a column 0.80m/s) with reactor top superficial linear velocity in a column
Mode, the ammoxidation reaction as described below for carrying out propylene.Structure of reactor other than reactor inside diameter is same as Example 1
Condition.As a result, the use of the contacting efficiency (η) that preceding formulae calculates being 70%, the catalyst amount of dispersing is 3.8kg/h, reactor
The space density of catalyst in top is 24kg/m3.In addition, confirmation is internal when reactor stops, as a result on top and lower part
Between coupling part there is no the accumulation of apparent catalyst.
[comparative example 4]
Propylene, ammonia and air are supplied to upper inner diameter 10.5m, lower inner diameter 8m (D1/D2=1.313, A1/A2=
1.88), the inner wall with plumb line of the coupling part between top and lower part be formed by angle be 30 °), length 20m it is vertical
The fluidized-bed reactor 1-5 of cylinder type is 0.57m/s's (lower part superficial linear velocity in a column 1.07m/s) with reactor top superficial linear velocity in a column
Mode, the ammoxidation reaction as described below for carrying out propylene.Structure of reactor other than reactor inside diameter is same as Example 1
Condition.As a result, the use of the contacting efficiency (η) that preceding formulae calculates being 70%, the catalyst amount of dispersing is 1.5kg/h, reactor
The space density of catalyst in top is 47kg/m3.In addition, confirmation is internal when reactor stops, as a result on top and lower part
Between coupling part there is no the accumulation of apparent catalyst.Although without the variation that contacting efficiency, catalyst disperse, on
Portion's tower diameter increases, therefore evaluation space time yield is poor, space efficiency is deteriorated.
[comparative example 5]
Propylene, ammonia and air are supplied to upper inner diameter 8.7m, lower inner diameter 8m (D1/D2=1.088, A1/A2=
1.18), the inner wall with plumb line of the coupling part between top and lower part be formed by angle be 30 °), length 20m it is vertical
The fluidized-bed reactor 1-6 of cylinder type is 0.68m/s's (lower part superficial linear velocity in a column 0.80m/s) with reactor top superficial linear velocity in a column
Mode, the ammoxidation reaction as described below for carrying out propylene.Structure of reactor other than reactor inside diameter is same as Example 1
Condition.As a result, the use of the contacting efficiency (η) that preceding formulae calculates being 70%, the catalyst amount of dispersing is 2.0kg/h, reactor
The space density of catalyst in top is 73kg/m3.In addition, confirmation is internal when reactor stops, as a result on top and lower part
Between coupling part there is no the accumulation of apparent catalyst.
[comparative example 6]
Propylene, ammonia and air are supplied to upper inner diameter 8.7m, lower inner diameter 8m (D1/D2=1.088, A1/A2=
1.18), the inner wall with plumb line of the coupling part between top and lower part be formed by angle be 30 °), length 20m it is vertical
The fluidized-bed reactor 1-6 of cylinder type is 0.57m/s's (lower part superficial linear velocity in a column 0.67m/s) with reactor top superficial linear velocity in a column
Mode, the ammoxidation reaction as described below for carrying out propylene.Structure of reactor other than reactor inside diameter is same as Example 1
Condition.As a result, the use of the contacting efficiency (η) that preceding formulae calculates being 59%, the catalyst amount of dispersing is 1.5kg/h, reactor
The space density of catalyst in top is 47kg/m3.In addition, confirmation is internal when reactor stops, as a result on top and lower part
Between coupling part there is no the accumulation of apparent catalyst.
The evaluation result of above-described embodiment 1~3 and comparative example 1~6, which summarizes, is shown in the following table 1.
[table 1]
Industrial availability
The utility model can be effectively utilized when implementing fluidized-bed reaction using fluidized bed reaction.
Claims (6)
1. a kind of fluidized bed reaction, which is characterized in that it has reactor, and the reactor has storage flowable
The inner space of catalyst, and there is the cooling coil for autoreaction gas removal heat in the inner space and be used for
Autoreaction gas separates and recovers the cyclone separator of the catalyst,
Using the height of the lowest point of the inner space as benchmark, by the mean height of the inlet portion lower end of the cyclone separator
The internal diameter that degree is set as the reactor at h, height h is set as the reaction at upper inner diameter D1, h/2~h/4 height h '
When the mean inside diameter of device is set as lower inner diameter D2, D1/D2 be more than 1.000 and for 1.310 hereinafter,
Effective sectional area at the height h is set as the average effective sectional area at top effective sectional area A1, the height h '
When being set as lower part effective sectional area A2, A1/A2 is more than 1.18 and is 1.88 or less.
2. fluidized bed reaction according to claim 1, which is characterized in that the reactor is also equipped with to the inside
Space imports multiple unstrpped gas dispersers of unstrpped gas,
The lowest point of the inner space is the point being configured on the nozzle upper surface of the unstrpped gas disperser of extreme lower position.
3. fluidized bed reaction according to claim 1 or 2, which is characterized in that the lower inner diameter D2 be 3m~
10m。
4. fluidized bed reaction according to claim 1 or 2, which is characterized in that the lower part effective sectional area A2 is
6m2~70m2。
5. fluidized bed reaction according to claim 1 or 2, which is characterized in that the inlet portion of the cyclone separator
The average height h of lower end is 10m~25m.
6. fluidized bed reaction according to claim 1 or 2, which is characterized in that the reactor is from the height h
To the region of h ' at least part have by internal diameter decrescence in a manner of the part that is constituted,
It is 25 °~40 ° that the inner wall and plumb line of the part, which are formed by angle Θ,.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-100264 | 2017-05-19 | ||
| JP2017100264A JP6427225B1 (en) | 2017-05-19 | 2017-05-19 | Fluid bed reactor and method for producing α, β-unsaturated nitrile |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN208340685U true CN208340685U (en) | 2019-01-08 |
Family
ID=64379273
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201820524374.7U Withdrawn - After Issue CN208340685U (en) | 2017-05-19 | 2018-04-13 | Fluidized bed reaction |
| CN201810330787.6A Active CN108940137B (en) | 2017-05-19 | 2018-04-13 | Fluidized bed reactor and method for producing alpha, beta-unsaturated nitrile |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810330787.6A Active CN108940137B (en) | 2017-05-19 | 2018-04-13 | Fluidized bed reactor and method for producing alpha, beta-unsaturated nitrile |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP6427225B1 (en) |
| CN (2) | CN208340685U (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108940137A (en) * | 2017-05-19 | 2018-12-07 | 旭化成株式会社 | The manufacturing method of fluidized bed reaction and 'alpha ', ' bela '-unsaturated nitrile |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020200274A (en) * | 2019-06-11 | 2020-12-17 | 旭化成株式会社 | Method for producing acrylonitrile |
| CN112823871A (en) * | 2019-11-20 | 2021-05-21 | 中国石油化工股份有限公司 | Fluidized bed reactor, heat removal water pipe and application of heat removal water pipe in acrylonitrile manufacture |
| WO2022214068A1 (en) * | 2021-04-09 | 2022-10-13 | 中国石油化工股份有限公司 | Heat removal pipe group, and application thereof in temperature control of fluidized-bed reactor and fabrication of unsaturated nitriles |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MXPA05011665A (en) * | 2003-05-09 | 2005-12-15 | Standard Oil Co | Fluidized bed reactor with gas cooler. |
| JP2005193172A (en) * | 2004-01-08 | 2005-07-21 | Daiyanitorikkusu Kk | Fluidized reaction method and method for producing acrylonitrile |
| CN101954264B (en) * | 2010-04-20 | 2012-06-27 | 南通泰禾化工有限公司 | Novel fluidized bed reactor for synthetizing m-phthalonitrile |
| JP6427225B1 (en) * | 2017-05-19 | 2018-11-21 | 旭化成株式会社 | Fluid bed reactor and method for producing α, β-unsaturated nitrile |
-
2017
- 2017-05-19 JP JP2017100264A patent/JP6427225B1/en active Active
-
2018
- 2018-04-13 CN CN201820524374.7U patent/CN208340685U/en not_active Withdrawn - After Issue
- 2018-04-13 CN CN201810330787.6A patent/CN108940137B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108940137A (en) * | 2017-05-19 | 2018-12-07 | 旭化成株式会社 | The manufacturing method of fluidized bed reaction and 'alpha ', ' bela '-unsaturated nitrile |
| CN108940137B (en) * | 2017-05-19 | 2021-07-27 | 旭化成株式会社 | Fluidized bed reactor and method for producing alpha, beta-unsaturated nitrile |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6427225B1 (en) | 2018-11-21 |
| CN108940137A (en) | 2018-12-07 |
| CN108940137B (en) | 2021-07-27 |
| JP2018192446A (en) | 2018-12-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN208340685U (en) | Fluidized bed reaction | |
| US6894183B2 (en) | Method for gas—solid contacting in a bubbling fluidized bed reactor | |
| US8128878B2 (en) | Gas-phase polymerization of alpha-olefin | |
| EP2966094B1 (en) | Olefin polymerization method | |
| CN106622044A (en) | Ammonia oxidation reactor and preparation method of nitrile compounds | |
| CN101448734A (en) | Method for producing chlorine by gas phase oxidation | |
| CN101687160A (en) | The method for preparing chlorine by multi step adiabatic gas phase oxidation | |
| CN101293637B (en) | Apparatus and method for producing chlorine gas with hydrogen chloride catalytic oxidation | |
| US6649130B1 (en) | Reaction process in hybrid reactor for propylene ammoxidation | |
| KR20120098834A (en) | Gas phase reaction method | |
| CN205672887U (en) | Inner member and fluidized-bed reactor for fluidized-bed reactor | |
| CN209597140U (en) | Fluidized bed reaction | |
| CN107243300A (en) | A kind of preparation facilities of cyanalcohol and preparation method thereof | |
| EP2363203B1 (en) | Method of reaction using heat-exchange type reactor | |
| CN102753586B (en) | Process for the gas phase polymerisation of olefins | |
| Hu et al. | Ammoxidation of propylene to acrylonitrile in a bench-scale circulating fluidized bed reactor | |
| US20060182673A1 (en) | Apparatus for heterogeneous catalysed reactions | |
| CS202004B2 (en) | Method of producing melamine by heating of urea | |
| CN106006673B (en) | Prepare the device of hydrogen cyanide | |
| CN102276396A (en) | Method for supplementing catalyst into methanol-to-olefin reaction and regeneration system | |
| CN206492486U (en) | Produce free-running assembled tube type scaling -up device | |
| CN1875085B (en) | A method for converting a liquid feed material into a vapor phase product | |
| Elnashaie et al. | The use of mathematical and computer models to explore the applicability of fluidized bed technology for highly exothermic catalytic reactions: II-oxidative dehydrogenation of ethylbenzene to styrene | |
| Han et al. | Conversion of hydrogen chloride to chlorine by catalytic oxidation in a two-zone circulating fluidized bed reactor | |
| CN105315119B (en) | The method of methanol-to-olefins based on high density reactors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| AV01 | Patent right actively abandoned |
Granted publication date: 20190108 Effective date of abandoning: 20210727 |
|
| AV01 | Patent right actively abandoned |
Granted publication date: 20190108 Effective date of abandoning: 20210727 |
|
| AV01 | Patent right actively abandoned | ||
| AV01 | Patent right actively abandoned |