CN106917163B - A kind of hydrocarbon cracking prepares the reaction system and its processing method and purposes of carbon fiber - Google Patents
A kind of hydrocarbon cracking prepares the reaction system and its processing method and purposes of carbon fiber Download PDFInfo
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- CN106917163B CN106917163B CN201710145130.8A CN201710145130A CN106917163B CN 106917163 B CN106917163 B CN 106917163B CN 201710145130 A CN201710145130 A CN 201710145130A CN 106917163 B CN106917163 B CN 106917163B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
- D01F9/133—Apparatus therefor
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
- D01F9/1271—Alkanes or cycloalkanes
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/127—Carbon filaments; Apparatus specially adapted for the manufacture thereof by thermal decomposition of hydrocarbon gases or vapours or other carbon-containing compounds in the form of gas or vapour, e.g. carbon monoxide, alcohols
- D01F9/1271—Alkanes or cycloalkanes
- D01F9/1272—Methane
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Abstract
The present invention provides reaction systems and its processing method and purposes that a kind of hydrocarbon cracking prepares carbon fiber, the reaction system includes the concatenated two-dimentional fixed bed reactors of at least three, the material inlet of each two dimension fixed bed reactors is equipped with entrance three-way diverter valve, the material outlet of each two dimension fixed bed reactors is equipped with outlet three-way diverter valve and shut-off valve, the reaction mass entrance pipe of reaction system is connected by entrance three-way diverter valve with the entrance of each two-dimentional fixed bed reactors, the reacting material outlet pipeline of reaction system is connected by outlet three-way diverter valve with the outlet of each two-dimentional fixed bed reactors, at least one two-dimentional fixed bed reactors is standby reactor in the two dimension fixed bed reactors.System and method for of the present invention realizes interval catalysis carbon distribution continuous reaction by way of the reactor of switching, and is able to maintain that stable high hydrocarbon resolution ratio, is suitable for a variety of carbon raw materials, simple process.
Description
Technical field
Hydrocarbon oxidation catalyst of the present invention cracks field, is related to the reaction system that a kind of hydrocarbon cracking prepares carbon fiber
System and its processing method and purposes more particularly to a kind of utilize switch reaction principle, scale continuous production carbon nano-fiber
Reaction system and its processing method and purposes.
Background technique
Carbon fiber has low-density, high ratio modulus, high specific strength and high conduction performance, can be used as catalyst carrier, lithium
Ion battery anode, electrode for capacitors, high-efficiency adsorbent and structural reinforcement material etc. are the hot spots of investigation of materials in recent years.It is raw
The industrial method for producing carbon fiber is the method for gas phase catalysis pyrolysis carbon compound, that is, the chemical gaseous phase being widely used
Deposition method, this method are catalyst using or mixtures thereof iron, cobalt, nickel, in a hydrogen atmosphere catalytic cracking of hydrocarbon
Or carbon monoxide, and Carbon deposition is made to obtain carbon nano-fiber in catalyst particle surface.
Currently, both at home and abroad about carbon fiber preparation and application research it is more, as CN 1389606A, CN 1517458A,
CN 1793451 and CN 1886537A report the carbon fiber product for how preparing related pattern and structure.It is continuous in scale
In terms of metaplasia produces carbon fiber product, CN 101027434A and CN 102086537A are all based on catalyst and carbon source precursor (carbon
Hydrogen compound) it is blended in high-temperature region and carries out cartalytic decomposition effect and finally by separation obtain corresponding product.But these techniques
It is the reaction of interval carbon distribution, it can not continuous production, it is also difficult to realize high hydrocarbon resolution ratio and carbon fiber yield, and
The collection of product with separate it is also relatively difficult.
Summary of the invention
For existing hydrocarbon oxidation catalyst cracking prepare existing for carbon fiber product can not continuous production, and be difficult to realize
The problems such as collection of high hydrocarbon resolution ratio and carbon fiber yield and product is with difficulty is separated, the present invention provides
A kind of hydrocarbon cracking prepares the reaction system and its processing method and purposes of carbon fiber.System and method for of the present invention
Realized by way of the reactor of switching interval catalysis carbon distribution continuous reaction, be suitable for a variety of carbon raw materials, simple process, with
Other gas separation process couple the optimization process to form comprehensive utilization of energy.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides the reaction system that a kind of hydrocarbon cracking prepares carbon fiber, the reaction
System includes the concatenated two-dimentional fixed bed reactors of at least three, and the material inlet of each two dimension fixed bed reactors is equipped with entrance
The material outlet of three-way diverter valve, each two dimension fixed bed reactors is equipped with outlet three-way diverter valve and shut-off valve, reaction system
Reaction mass entrance pipe by entrance three-way diverter valve with two dimension fixed bed reactors entrance be connected, reaction system it is anti-
Material outlet pipeline is answered to be connected by outlet three-way diverter valve with the outlet of two-dimentional fixed bed reactors, the two dimension fixed bed is anti-
Answering the two-dimentional fixed bed reactors of at least one in device is standby reactor.
Wherein, the number of two-dimentional fixed bed reactors can be for 3,4,5,6,7,8 or 9 and more,
It is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
In the present invention, the quantity of two-dimentional fixed bed reactors is designed according to needs of production；But in whole system
Need to guarantee at least one two-dimentional fixed bed reactors as standby reactor；The standby reactor is for carrying out product
Collection and raw catelyst replacement, i.e., other two dimension fixed bed reactors reacted when, be in stand-by state,
After two-dimentional fixed bed reactors inactivation in reacted, standby reactor is used to replace the two-dimentional fixed bed reaction of the inactivation
Device, to guarantee being carried out continuously for reaction.
In reaction operational process, each two-dimentional fixed bed reactors in addition to standby reactor are used in series, and are made hydrocarbon
Compound reaches thermodynamical equilibrium conversion ratio at the reaction temperatures.
In the present invention, the two-dimentional fixed bed reactors in the reaction and the switching between standby reactor pass through triple valve
Rotation realize.
It is used as currently preferred technical solution below, but not as the limitation of technical solution provided by the invention, passes through
Following technical scheme can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, the two dimension fixed bed reactors are external-heat two dimension fixed bed reaction
Device.
As currently preferred technical solution, the two dimension fixed bed reactors are rectangular parallelepiped structure, are internally provided with
At least 2 layers of catalyst bed place catalyst sample slot on every layer of catalyst bed.Wherein, the number of plies of the catalyst bed
Can be for 2 layers, 3 layers, 4 layers, 5 layers, 6 layers, 7 layers, 8 layers, 9 layers or 10 layers and more, it is not limited to cited numerical value, it should
Other unlisted numerical value are equally applicable in numberical range.
In the present invention, the two dimension fixed bed reactors are rectangular parallelepiped structure, and length is denoted as a, and width is denoted as b, thickness
It is denoted as d.
As currently preferred technical solution, the width b of the two dimension fixed bed reactors and the ratio of thickness d are
(10~20): 1, such as 10:1,11:1,12:1,13:1,14:1,15:1,16:1,17:1,18:1,19:1 or 20:1 etc., but simultaneously
It is not limited only to cited numerical value, other unlisted numerical value are equally applicable in the numberical range, preferably (12~16): 1.
In the present invention, it is described two dimension fixed bed reactors width and thickness need to control in a certain range, if width b and
The ratio of thickness d is excessive, i.e., reactor is wide, will lead to the increase of reactor difficulty of processing, and internal gas distributing homogeneity drops
It is low；If width b and the ratio of thickness d are too small, i.e., reactor is blocked up, reaction heat transfer can be made to be suppressed, it is difficult to guarantee reactor
Internal temperature uniformity, and then finally influence hydrocarbon resolution ratio.
Preferably, the ratio of the length a and width b of the two-dimentional fixed bed reactors are (1~10): 1, such as 1:1,2:
1,3:1,4:1,5:1,6:1,7:1,8:1,9:1 or 10:1 etc., it is not limited to cited numerical value, in the numberical range its
His unlisted numerical value is equally applicable, preferably (1~5): 1.
In the present invention, it is described two dimension fixed bed reactors length and width need to control in a certain range, if length a and
The ratio of width b is excessive, i.e., reactor is too long, can make gas displacement time course, and detaching products are difficult；If length a and width b
Ratio it is too small, i.e., reactor is too short, can make gas residence time section, it is difficult to reach abundant reaction effect, hydrogen in gaseous product
Content is relatively low.
Catalyst sample slot interval setting as currently preferred technical solution, on every layer of catalyst bed.
During the reaction, reaction gas is passed through reaction from reactor head to two dimension fixed bed reactors of the present invention
Device contacts with the catalyst of each layer setting from top to bottom, makes catalyst that reduction and carbon distribution successively be undergone to react complete to catalyst
It loses activity.
Preferably, the number of catalyst sample slot is 2~5 on every layer of catalyst bed, such as 2,3,4
It is a or 5 etc., preferably 2~3.
Preferably, the ratio of the length m and width n of the catalyst sample slot are (5~20): 1, such as 5:1,7:1,9:
1,10:1,13:1,15:1,17:1,19:1 or 20:1 etc., it is not limited to cited numerical value, in the numberical range other
Unlisted numerical value is equally applicable.
In the present invention, the setting of the catalyst sample slot are as follows: the length of catalyst sample slot and two-dimentional fixed bed reaction
The setting of device length parallel direction.
Preferably, carbon deposition catalyst is laid in the catalyst sample slot.
Preferably, the laying depth of the carbon deposition catalyst be 1mm~10mm, such as 1mm, 2mm, 3mm, 4mm, 5mm,
6mm, 7mm, 8mm, 9mm or 10mm etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range
It is equally applicable.
In the present invention, the carbon deposition catalyst laying depth do not answer it is blocked up, it is blocked up that unit mass catalyst can be made to be generated
Carbon fiber Mass lost, reduce yield, while also should ensure that dosage required for reaction, therefore also can not be excessively thin.
As currently preferred technical solution, the opposite two sides of the two dimension fixed bed reactors is fired equipped with associated gas
Burn heating unit.
The associated gas combustion heat supplying unit combustion parts unstripped gas reaches reactor temperature and maintains accordingly to be catalyzed
The active temperature of agent realizes the continuous process of highly endothermic inactivation reaction.
Preferably, the opposite two sides is two planes of length a and width the b composition of two-dimentional fixed bed reactors.
Second aspect, the present invention provides the processing method of above-mentioned reaction system, the processing method are as follows:
(a) using hydrocarbon as unstripped gas, unstripped gas is passed through the two-dimensional solid being sequentially connected in series in addition to standby reactor
It is contacted in fixed bed reactor with catalyst and carries out hydrocarbon cracking reaction；
(b) when the catalyst in one of two-dimentional fixed bed reactors in the concatenated two-dimentional fixed bed reactors
It is switched over after losing activity completely, replaces the completely deactivated two-dimentional fixed bed reaction of the catalyst with standby reactor
Device continues hydrocarbon cracking reaction；
(c) carbon fiber reacted in the completely deactivated two-dimentional fixed bed reactors of the catalyst is collected to produce
Object loads the standby reactor after new catalyst as reaction system and continues to use；
Repeat the above steps (a)~step (c), continuous production carbon fiber product.
In the present invention, the concatenated two-dimentional fixed bed reactors are carried out continuously reaction, can be anti-by interval inactivation carbon distribution
It should realize serialization, but also the fully effective participation reaction of catalyst may be implemented, until reaction inactivation, carbon deposition quantity maximize,
The utilization rate of catalyst is improved to greatest extent.
Carbon fiber product produced by the present invention can be used for catalyst carrier, macromolecule filler, electrostatic shielding materials or
The fields such as waste water adsorbent material.
As currently preferred technical solution, flow velocity of the unstripped gas described in step (a) in reactor is 1cm/min
~10cm/min, such as 1cm/min, 2cm/min, 3cm/min, 4cm/min, 5cm/min, 6cm/min, 7cm/min, 8cm/
Min, 9cm/min or 10cm/min etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range
It is equally applicable.
Preferably, the catalyst in the two-dimentional fixed bed reactors is that any one in iron series, cobalt system or nickel system is hydrocarbon
Compound cracks fine catalyst.
Preferably, the catalyst in the two-dimentional fixed bed reactors is nanometer Fe2O3Catalyst, cobalt oxide catalyst or
Any one in nickel oxide catalyst or at least two combination.In the present invention, the catalyst is not limited in above-mentioned enumerate
Catalyst, can be selected according to needs of production.
Preferably, the reaction temperature of the two-dimentional fixed bed reactors is 500 DEG C~1000 DEG C, for example, 500 DEG C, 550 DEG C,
600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C or 1000 DEG C etc., it is not limited to cited
Numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, the reaction time of the single two-dimentional fixed bed reactors is 3h~for 24 hours, for example, 4h, 6h, 8h, 10h,
12h, 14h, 16h, 18h, 20h, 22h etc., it is not limited to cited numerical value, other interior unlisted numbers of the numberical range
It is worth equally applicable.
The third aspect, the present invention provides the purposes of above-mentioned reaction system, the reaction system is applied to contain nytron
The waste gases catalytic pyrolysis of object prepares carbon fiber process.Meanwhile it being also applied for during petroleum refining process and coal chemical industry
The Pintsch process carbon fiber process of dry gas, pyrolysis gas and the gas that gasifies.
Preferably, the waste gases of the hydrocarbon-containiproducts are oil field gas, coal-bed gas gas, biofermentation biogas
Any one in device in Gas or at least two combination.The waste gases of hydrocarbon-containiproducts of the present invention are not limited in
Above-mentioned gas, but other equally applicable carbon sources other prepare the reaction process of carbon fiber.
Compared with prior art, the invention has the following advantages:
The present invention is transformed by the structure to two-dimentional fixed bed reactors, using external-heat two dimension fixed bed reactors
It is reacted, interval catalysis carbon distribution continuous reaction is realized in the switching for carrying out reactor during the reaction, finally improves carbon
Hydrogen compound resolution ratio and carbon fiber yield make hydrocarbon resolution ratio up to 50%~80%, and carbon fiber yield is reachable
30%~70%, at the same solve the problems, such as product collection and separate difficulty.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the reaction system that hydrocarbon cracking of the present invention prepares carbon fiber；
Fig. 2 is the structural representation for the reaction system that hydrocarbon cracking prepares carbon fiber described in the embodiment of the present invention 1
Figure；
Fig. 3 is to replace deactivated two-dimentional fixed bed reactors with standby reactor described in the embodiment of the present invention 1
Schematic diagram,
Fig. 4 is the structural schematic diagram of two dimension fixed bed reactors described in the embodiment of the present invention 1；
Wherein, 1- two dimension fixed bed reactors, 2- entrance three-way diverter valve, 3- export three-way diverter valve, 4- shut-off valve, 5-
Catalyst sample slot, 6- associated gas combustion heat supplying unit.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention, this
Invention protection scope is subject to claims.
As shown in Figure 1, specific embodiment of the invention part, which provides a kind of hydrocarbon cracking, prepares the anti-of carbon fiber
System is answered, the reaction system includes the concatenated two-dimentional fixed bed reactors 1 of at least three, each two dimension fixed bed reactors
Material inlet is equipped with entrance three-way diverter valve 2, and the material outlet of each two dimension fixed bed reactors 1 is equipped with outlet three-way diverter valve
3 and shut-off valve 4, the reaction mass entrance pipe of reaction system passes through entrance three-way diverter valve 2 and two-dimentional fixed bed reactors 1
Entrance is connected, and the reacting material outlet pipeline of reaction system is gone out by outlet three-way diverter valve 3 and two-dimentional fixed bed reactors 1
Mouth is connected, at least one two-dimentional fixed bed reactors 1 is standby reactor 1-1 in the two dimension fixed bed reactors 1.
The processing method of the system are as follows:
(a) using hydrocarbon as unstripped gas, unstripped gas is passed through the two dimension being sequentially connected in series in addition to standby reactor 1-1
It is contacted in fixed bed reactors 1 with catalyst and carries out hydrocarbon cracking reaction；
(b) when the catalysis in one of two-dimentional fixed bed reactors 1 in the concatenated two-dimentional fixed bed reactors 1
Agent switches over after losing activity completely, and it is fixed to replace the completely deactivated two dimension of the catalyst with standby reactor 1-1
Bed reactor 1, continues hydrocarbon cracking reaction；
(c) carbon fiber reacted in the completely deactivated two-dimentional fixed bed reactors 1 of the catalyst is collected to produce
Object loads the standby reactor after new catalyst as reaction system and continues to use；
Repeat the above steps (a)~step (c), continuous production carbon fiber product.
The following are typical but non-limiting embodiments of the invention:
Embodiment 1:
As shown in Fig. 2, the reaction system that a kind of hydrocarbon cracking prepares carbon fiber is present embodiments provided, it is described anti-
Answering system includes 3 concatenated two-dimentional fixed bed reactors 1, and one of two dimension fixed bed reactors 1 are standby reactor 1-
1, the material inlet of each two dimension fixed bed reactors 1 is equipped with entrance three-way diverter valve 2, each two dimension fixed bed reactors 1
Material outlet is equipped with outlet three-way diverter valve 3 and shut-off valve 4, and the reaction mass entrance pipe of system is answered to turn to by entrance threeway
Valve 2 is connected with the entrance of two-dimentional fixed bed reactors 1, and the reacting material outlet pipeline of reaction system passes through outlet three-way diverter valve
3 are connected with an outlet for two-dimentional fixed bed reactors 1.
Wherein, the two-dimentional fixed bed reactors 1 are external-heat two dimension fixed bed reactors.
As shown in figure 4, the two dimension fixed bed reactors 1 are rectangular parallelepiped structure, 7 layers of catalyst bed are internally provided with,
Catalyst sample slot 5 is placed on every layer of catalyst bed；The width b of the two dimension fixed bed reactors 1 and the ratio of thickness d are
The ratio of 15:1, the length a and width b of the two dimension fixed bed reactors 1 are 3:1；Catalyst on every layer of catalyst bed
The interval of sample cell 5 is arranged, and the number of catalyst sample slot 5 is 2~3 on every layer of catalyst bed, catalyst sample slot 5
The ratio of length m and width n are 10:1, are laid with carbon deposition catalyst in catalyst sample slot 5, the laying depth of carbon deposition catalyst is
Two planes of 5mm, two-dimentional 1 length a of fixed bed reactors and width b composition are equipped with associated gas combustion heat supplying unit 6.
Embodiment 2:
Present embodiments provide the processing side that hydrocarbon cracking described in embodiment 1 prepares the reaction system of carbon fiber
Method, specific as follows:
After the present embodiment passes through pressure-variable adsorption and deep desulfuration with oil well associated gas, corresponding hydrocarbon conduct is obtained
Carbon distribution unstripped gas, wherein methane content is 93wt%, ethane content 5wt%, CO2For 2wt%, restore sulfur content 1ppm with
Under.With nanometer α-Fe2O3Make catalyst.
Unstripped gas is passed through 2 concatenated two-dimentional fixed bed reactions in addition to standby reactor 1-1 with the flow velocity of 5cm/min
It in device 1, is contacted with catalyst and carries out hydrocarbon cracking reaction, control the temperature of two-dimentional fixed bed reactors 1 at 730 DEG C,
Reaction time in single two dimension fixed bed reactors 1 is 30h, after reaction, when one of two-dimentional fixed bed reactors 1
After middle catalyst complete deactivation, the completely deactivated two-dimentional fixed bed reactors of the catalyst are replaced with standby reactor 1-1
1, continue hydrocarbon cracking reaction.
The carbon fiber product reacted in the completely deactivated two-dimentional fixed bed reactors 1 of the catalyst is collected,
Carbon deposition quantity of catalyst is 20 times of original catalyst total weight, loads the standby reactor after new catalyst as reaction system
1-1 is continued to use, as shown in Figure 3；
It repeats the above process, continuous production carbon fiber product.
Hydrocarbon resolution ratio is 70% in the present embodiment, and carbon fiber is selectively 100%, and exporting hydrogen concentration is stablized
70%.
Embodiment 3:
The reaction system that a kind of hydrocarbon cracking prepares carbon fiber is present embodiments provided, the reaction system includes
5 concatenated two-dimentional fixed bed reactors 1, one of two dimension fixed bed reactors 1 are standby reactor 1-1, each two dimension
The material inlet of fixed bed reactors 1 is equipped with entrance three-way diverter valve 2, and the material outlet of each two dimension fixed bed reactors 1 is set
There are outlet three-way diverter valve 3 and shut-off valve 4, the reaction mass entrance pipe of system is answered to pass through entrance three-way diverter valve 2 and two dimension
The entrance of fixed bed reactors 1 is connected, and the reacting material outlet pipeline of reaction system passes through outlet three-way diverter valve 3 and two-dimensional solid
The outlet of fixed bed reactor 1 is connected.
The two dimension fixed bed reactors 1 are equipped with 8 layers of catalyst bed in addition to inside, and the ratio of width b and thickness d is
12:1, the ratio of the length a and width b of the two dimension fixed bed reactors 1 are 5:1, catalyst sample on every layer of catalyst bed
The number of product slot 5 is 3~5, and the ratio of the length m and width n of catalyst sample slot 5 is 20:1, in catalyst sample slot 5
It is laid with carbon deposition catalyst, the laying depth of carbon deposition catalyst is outside 10mm, and other structures are in the same manner as in Example 1.
Embodiment 4:
Present embodiments provide the processing side that hydrocarbon cracking described in embodiment 3 prepares the reaction system of carbon fiber
Method, the processing method are in the same manner as in Example 2.
Hydrocarbon resolution ratio is 65% in the present embodiment, and carbon fiber is selectively 100%, and long-time stable operates out
Mouth density of hydrogen is 68%.
Embodiment 5:
Reaction system and its processing method that a kind of hydrocarbon cracking prepares carbon fiber are present embodiments provided, it is described
System is 16:1 in addition to two-dimentional 1 width b of fixed bed reactors and the ratio of thickness d, the length of the two dimension fixed bed reactors 1
The ratio of a and width b are 10:1, and the ratio of the length m and width n of catalyst sample slot 5 are 5:1,5 middle berth of catalyst sample slot
If carbon deposition catalyst, the laying depth of carbon deposition catalyst is outside 1mm, and other structures are in the same manner as in Example 1.
Its processing method is 10cm/min in addition to the flow velocity of unstripped gas, controls the temperature of two-dimentional fixed bed reactors 1 550
It is DEG C outer, other processes with it is in the same manner as in Example 2.
Hydrocarbon resolution ratio is 55% in the present embodiment, and carbon fiber is selectively 100%, and long-time stable operates out
Mouth density of hydrogen is 66%.
Embodiment 6:
Reaction system and its processing method that a kind of hydrocarbon cracking prepares carbon fiber are present embodiments provided, it is described
System is 20:1 in addition to two-dimentional 1 width b of fixed bed reactors and the ratio of thickness d, the length of the two dimension fixed bed reactors 1
The ratio of a and width b are 2:1, and carbon deposition catalyst is laid in catalyst sample slot 5, and the laying depth of carbon deposition catalyst is 2mm
Outside, other structures are in the same manner as in Example 1.
Its processing method is 2cm/min in addition to the flow velocity of unstripped gas, controls the temperature of two-dimentional fixed bed reactors 1 950
It is DEG C outer, other processes with it is in the same manner as in Example 2.
Hydrocarbon resolution ratio is 60% in the present embodiment, and carbon fiber is selectively 100%, and long-time stable operates out
Mouth density of hydrogen is 67%.
Comparative example 1:
This comparative example provides the reaction system that a kind of hydrocarbon cracking prepares carbon fiber, and the system is in addition to including
3 two-dimentional fixed bed reactors 1, described 3 two-dimentional fixed bed reactors 1 are arranged in parallel, and reaction are simultaneously participated in, without spare reaction
Outside device, other structures are in the same manner as in Example 1.
The processing method of the system are as follows:
With in embodiment 2 raw material and catalyst reacted, 3 two-dimentional fixed bed reactors 1 are reacted simultaneously, instead
It answers condition in the same manner as in Example 2, prepares carbon fiber.
Hydrocarbon resolution ratio is to be reduced to 10% from 70% in this comparative example, and carbon fiber is selectively 100%, outlet
Density of hydrogen is reduced to 20% from 70%, is unstable operating process.
Comparative example 2:
This comparative example provides the reaction system that a kind of hydrocarbon cracking prepares carbon fiber, removes in the reaction system
Two-dimentional fixed bed reactors 1 (it is anti-to be different from heretofore described two-dimentional fixed bed using traditional fixed bed reactors
Answer device) outside, other structures be in embodiment 1 it is identical.
The processing method of the system is in the same manner as in Example 2.
Hydrocarbon resolution ratio is 30% in this comparative example, and carbon fiber is selectively 100%, and density of hydrogen is lower than
30%, reactor center differs 100 DEG C with lip temperature.
Comparative example 3:
This comparative example provides the reaction system and its processing method that a kind of hydrocarbon cracking prepares carbon fiber, described
In addition to two-dimentional 1 width b of fixed bed reactors and the ratio of thickness d are 5:1 in system, i.e., reactor is blocked up outer, and other structures are equal
It is in the same manner as in Example 1.
The processing method of the system is in the same manner as in Example 2.
Hydrocarbon resolution ratio is 58% in this comparative example, and carbon fiber is selectively 100%, density of hydrogen 55%.
Comparative example 4:
This comparative example provides the reaction system and its processing method that a kind of hydrocarbon cracking prepares carbon fiber, described
In addition to two-dimentional 1 width b of fixed bed reactors and the ratio of thickness d are 25:1 in system, i.e., reactor is wide outer, and other structures are equal
It is in the same manner as in Example 1.
The processing method of the system is in the same manner as in Example 2.
Hydrocarbon resolution ratio is 62% in this comparative example, and carbon fiber is selectively 100%, density of hydrogen 65%.
Comparative example 5:
This comparative example provides the reaction system and its processing method that a kind of hydrocarbon cracking prepares carbon fiber, described
In system in addition to be laid in catalyst sample slot 5 carbon deposition catalyst with a thickness of 15mm, i.e., catalyst is laid with blocked up outer, other knots
Structure is in the same manner as in Example 1.
The processing method of the system is in the same manner as in Example 2.
Hydrocarbon resolution ratio is 62% in this comparative example, and carbon fiber is selectively 100%, density of hydrogen 60%.
The present invention be can be seen that with the result of comparative example based on the above embodiments by the knot to two-dimentional fixed bed reactors
Structure is transformed, and is reacted using external-heat two dimension fixed bed reactors, and the switching for carrying out reactor during the reaction is real
Now interval catalysis carbon distribution continuous reaction, finally improves the stability of hydrocarbon resolution ratio and carbon fiber yield, makes carbon
For hydrogen compound resolution ratio steadily in the long term 70%, exporting hydrogen concentration is higher than 50%, at the same solve the collection of product with separate
Difficulty is conducive to the utilization of hydrogen in tail gas.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (17)
1. the reaction system that a kind of hydrocarbon cracking prepares carbon fiber, which is characterized in that the reaction system includes at least 3
A concatenated two-dimentional fixed bed reactors (1), the material inlet of each two dimension fixed bed reactors (1) are turned to equipped with entrance threeway
Valve (2), the material outlet of each two dimension fixed bed reactors (1) are equipped with outlet three-way diverter valve (3) and shut-off valve (4), reaction
The reaction mass entrance pipe of system is connected by entrance three-way diverter valve (2) with the entrance of two-dimentional fixed bed reactors (1), instead
The reacting material outlet pipeline of system is answered to be connected by outlet three-way diverter valve (3) with the outlet of two-dimentional fixed bed reactors (1),
The two-dimentional fixed bed reactors (1) of at least one in the two dimension fixed bed reactors (1) are standby reactor (1-1)；
The two dimension fixed bed reactors (1) are rectangular parallelepiped structure, are internally provided at least 2 layers of catalyst bed, every layer of catalysis
Catalyst sample slot (5) are placed on agent bed；
Catalyst sample slot (5) on every layer of catalyst bed is spaced setting；
Carbon deposition catalyst is laid in the catalyst sample slot (5), the laying depth of the carbon deposition catalyst is 1mm~10mm；
The width b of the two dimension fixed bed reactors (1) and the ratio of thickness d are (10~20): 1, the two dimension fixed bed is anti-
The ratio for answering the length a and width b of device (1) is (1~10): 1.
2. reaction system according to claim 1, which is characterized in that the two dimension fixed bed reactors (1) are external-heat
Two-dimentional fixed bed reactors.
3. reaction system according to claim 1, which is characterized in that it is described two dimension fixed bed reactors (1) width b and
The ratio of thickness d is (12~16): 1.
4. reaction system according to claim 1, which is characterized in that it is described two dimension fixed bed reactors (1) length a and
The ratio of width b is (1~5): 1.
5. reaction system according to claim 1, which is characterized in that catalyst sample slot on every layer of catalyst bed
(5) number is 2~5.
6. reaction system according to claim 5, which is characterized in that catalyst sample slot on every layer of catalyst bed
(5) number is 2~3.
7. reaction system according to claim 1, which is characterized in that the length m and width of the catalyst sample slot (5)
The ratio of n is (5~20): 1.
8. described in any item reaction systems according to claim 1, which is characterized in that described two dimension fixed bed reactors (1) phase
Pair two sides be equipped with associated gas combustion heat supplying unit (6).
9. reaction system according to claim 8, which is characterized in that the opposite two sides is two-dimentional fixed bed reactors
(1) two planes of length a and width b composition.
10. the processing method of -9 described in any item reaction systems according to claim 1, which is characterized in that the processing method
Are as follows:
(a) using hydrocarbon as unstripped gas, unstripped gas is passed through the two-dimensional solid being sequentially connected in series in addition to standby reactor (1-1)
It is contacted in fixed bed reactor (1) with catalyst and carries out hydrocarbon cracking reaction；
(b) when the catalysis in one of two-dimentional fixed bed reactors (1) in the concatenated two-dimentional fixed bed reactors (1)
Agent switches over after losing activity completely, replaces the completely deactivated two-dimensional solid of catalyst with standby reactor (1-1)
Fixed bed reactor (1), continues hydrocarbon cracking reaction；
(c) the carbon fiber product that reaction obtains in the completely deactivated two-dimentional fixed bed reactors (1) of the catalyst is collected,
The standby reactor after new catalyst as reaction system is loaded to continue to use；
Repeat the above steps (a)~step (c), continuous production carbon fiber product.
11. processing method according to claim 10, which is characterized in that unstripped gas described in step (a) is in the reactor
Flow velocity be 1cm/min~10cm/min.
12. processing method according to claim 10, which is characterized in that urging in the two dimension fixed bed reactors (1)
Agent is iron series, any one hydrocarbon cracks fine catalyst in cobalt system or nickel system.
13. processing method according to claim 12, which is characterized in that urging in the two dimension fixed bed reactors (1)
Agent is nanometer Fe2O3Any one in catalyst, cobalt oxide catalyst or nickel oxide catalyst or at least two combination.
14. processing method according to claim 10, which is characterized in that the reaction of the two dimension fixed bed reactors (1)
Temperature is 500 DEG C~1000 DEG C.
15. processing method according to claim 10, which is characterized in that the single two-dimentional fixed bed reactors (1)
Reaction time is 3h~for 24 hours.
16. the purposes of -9 described in any item reaction systems according to claim 1, which is characterized in that the reaction system application
Carbon fiber process is prepared in the waste gases catalytic pyrolysis of hydrocarbon-containiproducts.
17. the purposes of reaction system according to claim 15, which is characterized in that the discarded gas of the hydrocarbon-containiproducts
Body is the combination of any one in oil field gas, biofermentation biogas or device in Gas or at least two.
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| CN203565055U (en) * | 2013-08-16 | 2014-04-30 | 中国石油化工股份有限公司 | Tubular reactor |
| CN106147841A (en) * | 2015-04-22 | 2016-11-23 | 中国石化工程建设有限公司 | A kind of Heavy oil hydrogenation method |
| CN106475018A (en) * | 2015-08-27 | 2017-03-08 | 中国石化工程建设有限公司 | Fixed bed reactors and its gas distributor |
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| CN203565055U (en) * | 2013-08-16 | 2014-04-30 | 中国石油化工股份有限公司 | Tubular reactor |
| CN106147841A (en) * | 2015-04-22 | 2016-11-23 | 中国石化工程建设有限公司 | A kind of Heavy oil hydrogenation method |
| CN106475018A (en) * | 2015-08-27 | 2017-03-08 | 中国石化工程建设有限公司 | Fixed bed reactors and its gas distributor |
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