CN109843835A - The manufacturing method of alkane - Google Patents
The manufacturing method of alkane Download PDFInfo
- Publication number
- CN109843835A CN109843835A CN201780063374.XA CN201780063374A CN109843835A CN 109843835 A CN109843835 A CN 109843835A CN 201780063374 A CN201780063374 A CN 201780063374A CN 109843835 A CN109843835 A CN 109843835A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- alkane
- reaction
- supported
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C9/00—Aliphatic saturated hydrocarbons
- C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
- C07C9/06—Ethane
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C9/00—Aliphatic saturated hydrocarbons
- C07C9/02—Aliphatic saturated hydrocarbons with one to four carbon atoms
- C07C9/08—Propane
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention provides a kind of under conditions of inhibiting side reaction, impurity production quantity unevenness not to occur, the method for alkane that is stable by the high purity olefin that can be easy to get and efficiently manufacturing high-purity.To multiple granulars of the filling without catalytic activity in reaction tower (10), using at least part in the granular as the carrier for having supported catalyst, alkane is manufactured by the reaction of the alkene and hydrogen of the gas phase state in the presence of the catalyst in the reaction tower (10).The ratio 0.001% of the sum of the weight of the catalyst that the weight for the catalyst for supporting the carrier respectively is respectively supported relative to the respective weight of the carrier and the carrier is more than and less than 0.01%.
Description
Technical field
The present invention relates to the sides that the alkane of high-purity is manufactured by the hydrogenation reaction to alkene in the presence of catalyst
Method.
Background technique
In recent years, the demand to the high-purity alkane of high-purity ethane, high-purity propane etc. is gradually increased.For example, making
For the high-purity propane of the raw material of high-pressure resistant silicon carbide (SiC) semiconductor, in order to realize the high voltage of silicon carbide, it is desirable that contained
Some respective concentration of impurity is less than 1.0 volume ppm.
Manufacturing method as high-purity alkane, it is known that the method that distillation purifying is carried out to low-purity alkane.But
In this method, for separating, the scale of distillation equipment of impurity is big, investment is also big.Also, because of larger, the institute of equipment
Very more energy is needed when operating.Especially to including the case where propylene is distilled as the low-purity propane of impurity
Under, since the boiling-point difference of propane and propylene is smaller, it is difficult so carrying out purifying by distillation.
It is also known that manufacturing the method for propane by the hydrogenation reaction to liquid propylene in the presence of catalyst (specially
Sharp document 1).But in the case that the propylene of raw material is liquid phase, if material concentration is high, reaction heat becomes larger, it is difficult to heat is removed, by
It causes propylene to decompose in excessive temperature rising and becomes impurity, impurity concentration is got higher.Therefore, in order to by liquid phase feed
Hydrogenation reaction manufactures the alkane of high-purity, needs to make material concentration about 25% hereinafter, therefore efficiently manufacturing high-purity
Alkane be difficult.
Then, it proposes through the hydrogenation reaction of the alkene to gas phase state and manufactures alkane (patent document 2).This
When, the catalyst and alumina balls without catalytic activity etc. for supporting carrier are filled in reaction tower, by will be by catalyst
In the presence of hydrogenation reaction generate reaction heat to alumina balls etc. spread or conduct heat etc. and remove reaction heat.Whereby, it prevents
The decomposition of alkene caused by rising because of excessive temperature, reduces impurity concentration.In addition, with towards the gas stream in reaction tower
Downstream reduces alumina balls etc., increases the ratio of catalyst.Whereby, it reacts alkene and hydrogen effectively, prevents unreacted
Alkene is mixed into alkane, reduces impurity concentration.
Existing technical literature
Patent document
Patent document 1: No. 3509226 specifications of U.S. Patent No.
Patent document 2: Japanese Patent Laid-Open 2014-84285 bulletin
Summary of the invention
The technical problems to be solved by the invention
According to the method recorded in patent document 2, because using the alkene of gas phase as raw material, with the original for using liquid phase
The case where material, is compared, and can also easily remove reaction heat even if improving material concentration.But that there are impurity production quantities is uneven,
The problem of can not manufacturing to stability and high efficiency the alkane of high-purity.
Present invention aim to address reacting for alkene and hydrogen by gas phase state to manufacture in the method for alkane
The above-mentioned problems of the prior art.
Technical scheme applied to solve the technical problem
The present invention is a kind of method for manufacturing alkane, to fill multiple grains without catalytic activity into reaction tower
Shape component, using at least part in the granular as the carrier for having supported catalyst, by the reaction tower
The catalyst in the presence of gas phase state alkene and the method for hydrogen reacted to manufacture alkane, characterized in that make
The total weight of the catalyst of whole supported carriers is relative to the granular of the whole comprising the carrier
The ratio of the sum of total weight and whole total weights of the catalyst of the supported carrier 0.001% more than and less than
0.01%；The weight for the catalyst for supporting the carrier respectively is relative to the respective weight of the carrier and the carrier
The ratio of the sum of the weight of the catalyst respectively supported is 0.001% more than and less than 0.01%.
The present invention is based on discoveries below.
It is recorded in patent document 2 in the prior art, in the upstream region for reacting active gas stream, by alumina balls etc.
It is mixed with the carrier for having supported catalyst, makes the volume of alumina balls etc. relative to the volume of alumina balls etc. and supported catalysis
The ratio of the sum of the volume of whole carriers of agent is 90~99%.In the ratio of the alumina balls for not having catalytic activity in this way etc.
In the case where height, catalyst distribution is uneven in reaction tower, and admixture is also without reproducibility.In patent document 2, carrier
The sum of the weight of catalyst that the weight of the catalyst respectively supported is respectively supported relative to the respective weight of carrier and carrier
Ratio is 0.1~1.0%.Therefore, at the non-uniform position of catalyst distribution, reaction heat increases, due to due to local pyrexia
Caused excess temperature rises, and alkene decomposes and becomes impurity.Whereby, in the prior art, impurity production quantity generates uneven, nothing
Manufacture to method stability and high efficiency the alkane of high-purity.
In contrast, according to the present invention, it is respective relative to carrier by the weight for the catalyst for respectively supporting carrier
The ratio of the sum of the weight of catalyst that weight and carrier respectively support sets smaller than the above-mentioned prior art, is set as being less than
0.01%, reaction heat can be reduced, excessive temperature rises caused by preventing because of local pyrexia, can inhibit because the decomposition of alkene causes
Impurity generate, can prevent impurity production quantity from generating uneven.In addition, because do not need the granular for being not used as carrier, or can
Blending ratio is set smaller, so it is uneven to prevent impurity production quantity from generating.Pass through the catalyst for respectively supporting carrier
The sum of the weight of catalyst that is respectively supported relative to the respective weight of carrier and carrier of weight ratio be set as 0.001% with
On, it can make that the hydrogenation reaction of alkene definitely occurs, and can definitely prevent unreacted alkene to be mixed into as impurity
In manufactured alkane.
By the way that the granular all as the carrier for having supported the catalyst, to be made to alkene plus hydrogen
Reaction more definitely occurs, and unreacted alkene can be prevented to be mixed into manufactured alkane as impurity, and make to react
The distribution uniformity of catalyst in tower can definitely prevent impurity production quantity from generating uneven.
In the present invention, preferably make a part in the granular as the carrier for having supported the catalyst,
It is mixed with the rest part for the granular for not supporting the catalyst, rather than makes to be filled not in the reaction tower
The granular with catalytic activity all as the carrier for having supported the catalyst.
Whereby, the weight of the catalyst respectively supported in the carrier is relative to the respective weight of the carrier and institute
The ratio for stating the sum of weight of the catalyst that carrier respectively supports is 0.001% present invention more than and less than 0.01%
In, not catalyst-loaded grain not as carrier is also filled up even if not being only filled in reaction tower and having supported the carrier of catalyst
In the case where shape component, catalytic amount is also ensured that, make that the hydrogenation reaction of alkene definitely occurs, and can prevent unreacted
Alkene be mixed into as impurity in manufactured alkane.
The alkene and the preferred carbon number of alkane are respectively 2~4.That is, it is preferred that by propylene (C3H6) hydrogenation reaction come
Manufacture propane (C3H8), by ethylene (C2H4) hydrogenation reaction manufacture ethane (C2H6), by n-butene or isobutene
(C4H8) hydrogenation reaction manufacture butane (C4H10)。
The catalyst preferably comprises palladium, and the carrier is preferably aluminium oxide.
The purity of the alkane is preferably more than 99.99 volume %, more preferably more than 99.999 volume %.
Invention effect
In accordance with the invention it is possible to one kind be provided under conditions of inhibiting side reaction, impurity production quantity unevenness not to occur, by energy
The high purity olefin that is easy to get is stable and the method that efficiently manufactures the alkane of high-purity.
The brief description of accompanying drawing
Fig. 1 is the diagram showing the structure of the alkane manufacturing device of embodiments of the present invention.
Specific embodiment
Alkene of the alkane manufacturing device 1 shown in FIG. 1 by ethylene, propylene, n-butene or isobutene etc. as gas phase state
Hydrocarbon is supplied from olefin gas cylinder 2.The alkene of the supply is depressurized by the first pressure reducing valve 3, by first-class with flowmeter
Control valve 4 is adjusted to setting flow, imports in gas mixer 5.In addition, alkane manufacturing device 1 is by the hydrogen of gas phase state
It is supplied from hydrogen cylinder 6.The hydrogen of the supply is depressurized by the second pressure reducing valve 7, by the second flow control valve 8 for having flowmeter
It is adjusted to setting flow, is imported in gas mixer 5.In gas mixer 5 through mixed alkene and hydrogen as raw material from upper
Portion entrance 10a is imported in the reaction tower 10 of tubular.
The purity of manufactured alkane reduces in order to prevent, preferably as raw material alkene purity in 99.99 bodies
Product % or more.
Hydrogenation reaction to alkene is the reduction reaction reacted towards the progress of the direction of molal quantity reduction, so by that will compare
Hydrogen more than theoretical equivalence is supplied to reaction tower 10, can be improved reaction speed.In addition, supplying to the supply amount of the hydrogen of reaction tower 10
If the supply amount relative to alkene is lower than 1.00 times moles, the alkene as raw material is remained, if needing more than 2.00 times moles
Hydrogen is removed in subsequent handling, become trouble.Therefore, the supply amount of hydrogen relative to the supply amount of alkene be preferably 1.00~
2.00 times moles, more preferably 1.05~1.20 times moles.In addition, the purity of manufactured alkane reduces in order to prevent, it is excellent
The purity of the hydrogen for raw material is elected to be more than 99 volume %, more preferably more than 99.9 volume %.
Multiple granulars are filled in reaction tower 10.In the present embodiment, complete by what is filled in reaction tower 10
Portion's granular is as the carrier for having supported catalyst.
As catalyst, well known reducing catalyst can be used, such as the metal catalytics such as palladium, platinum, rhodium, ruthenium, nickel can be used
Agent uses palladium in present embodiment.As long as the carrier for the catalytically inactive that carrier can be catalyst-loaded, does not have material
There is restriction, uses aluminium oxide in present embodiment.The shape of carrier is limited using spherical shape, but to this without special in present embodiment
It is fixed, it is also possible to such as cylindric, graininess, size is set as average grain diameter 3mm in present embodiment, but to this without especially limit
It is fixed.In addition, carrier can support catalyst of more than two kinds.
The weight for the catalyst that carrier respectively supports relative in reaction tower 10 the respective weight of carrier and carrier respectively
The ratio of the sum of the weight of catalyst supported is set as 0.001% more than and less than 0.01%.That is, the respective weight of carrier is set
For ws, the weight for the catalyst that carrier respectively supports is set as wc, meet 0.001≤wc×100/(ws+wc) < 0.01.
In addition, the whole granulars filled in reaction tower 10 are used as having supported the carrier of catalyst, therefore all
Supported carrier catalyst total weight relative to whole granulars comprising carrier in reaction tower 10 total weight and
The sum of total weight of catalyst of whole supported carriers is 0.001% more than and less than 0.01%.
The reaction of the alkene and hydrogen of gas phase state in the presence of by catalyst in reaction tower 10 generates and is used as chain
Ethane, propane or butane of the gas phase state of alkane etc..In order to control the internal temperature of reaction tower 10, covered with cooling collar 11
Reaction tower 10 is arranged cooling device 12 to be attracted the refrigerant in cooling collar 11, be cooled down, and makes its reflux, with temperature
The internal temperature of 13 measurement reaction tower 10 of degree meter.The internal temperature of reaction tower 10 is set as the not liquefied temperature of alkane will not make
Reaction speed control become difficult, and be set as will not due to the decomposition of alkane the increased temperature of impurity.For example, in manufacture third
In the case that alkane is as alkane, the internal temperature of reaction tower 10 is preferably set to -42~250 DEG C, is more preferably set as 0~250 DEG C.
By the alkane generated to the hydrogenation reaction of alkene in reaction tower 10, from the lower openings of reaction tower 10
10b is discharged, and is imported into products pot 15 via the counterbalance valve 14 of the internal pressure for adjusting reaction tower 10, is utilized pressure gauge
The internal pressure of 16 measurement reaction towers 10.If the internal pressure of reaction tower 10 is excessively high, hydrogenation reaction is promoted, can but have
Reaction heat can be unable to control and impurity increases, and it is possible to which reaction gas occurs liquefaction and becomes liquid phase reactor, therefore preferably
Carry out suitable control.For example, the internal pressure of reaction tower 10 is preferably typically set in the case where manufacturing propane as alkane
0.0~0.5MPaG is more preferably set as 0.1~0.5MPaG.
The smaller the better result of gas flow rate and space velocity when can be obtained reduction reaction.For example, making in manufacture propane
In the case where alkane, the air velocity SV under standard state gas flow is preferably set to 1000/h hereinafter, being more preferably set as
500/h or less.By making space velocity in 1000/h hereinafter, hydrogenation reaction will not become inadequate, can prevent unreacted
The residual of raw material.
In order to analyze impurity contained in the alkane generated by hydrogenation reaction, will be arranged from the outlet 10b of reaction tower 10
A part of gas out imports gas chromatograph 17.
In the present embodiment, in order to separate hydrogen with the alkane that the reaction by alkene and hydrogen generates, setting cooling
Device 18 carries out cooling with the alkane to the gas phase imported in products pot 15, liquefies.Cooling temperature based on cooling device 18
It is set as than the low boiling point of alkane, higher than the boiling point of hydrogen.It is passed through in the state of not liquefying in alkane as hydrogen contained by impurity
It is discharged by the third flow control valve 19 with flowmeter from products pot 15, is separated with alkane, can be improved alkane whereby
Purity.In the present embodiment, the concentration of hydrogen contained in alkane is set as less than 1.0 volume ppm.Can also by recycling from
The hydrogen of alkane separation, returns it in reaction tower 10, to recycle as raw material.
Embodiment
(embodiment 1)
Using the alkane manufacturing device 1 of above embodiment, propane has been manufactured by the hydrogenation reaction to propylene.
Reaction tower 10 is made of stainless steel and internal diameter is 31mm.The packed height of granular in reaction tower 10 is set as
50cm.Using the whole granulars filled in reaction tower 10 as catalyst-loaded carrier.That is, having supported the whole of catalyst
The sum of the volume of carrier and the not catalyst-loaded volume of whole granulars are carried relative to the whole of catalyst have been supported
The ratio of the volume of body is 1 times.As the carrier for having supported catalyst, having used average grain diameter is the triumphant good strain formula meeting of NE of 3mm
The product of society (エ ヌ イ ー ケ system キ ャ ッ ト (strain)).Each carrier of the present embodiment is made of alpha-aluminium oxide, and has supported conduct
The palladium (Pd) of catalyst.The weight for the catalyst that carrier respectively supports respectively is supported relative to the respective weight of carrier and carrier
The ratio (hereinafter, " supporting rate " that the ratio is known as to the catalyst based on carrier) of the sum of the weight of catalyst is 0.001%.
The propylene that purity is more than 99.99 volume % is supplied from olefin gas cylinder 2, gas was imported with 1.0L/ minutes flows
In body mixer 5, the hydrogen that purity is more than 99.999 volume % is supplied from hydrogen cylinder 6, gas was imported with 1.1L/ minutes flows
In mixer 5.After propylene and hydrogen are mixed at room temperature in mixer 5, import in reaction tower 10.At this point, reaction tower 10
Internal pressure is set as 0.3MPaG, recycles 40 DEG C of temperature of water in cooling collar 11 as refrigerant.
Entrance 10a by the hydrogenation reaction to propylene in the reaction tower 10 under above-mentioned condition, in autoreaction tower 10
It rises and shows that maximum heating temperature is 230 DEG C at the position of distance 7cm.
The gas chromatograph 17 made by Shimadzu Corporation (Shimadzu Seisakusho Ltd. (strain)) is to from reaction tower 10
Impurity contained by the propane gas of outlet 10b discharge is analyzed, and in the impurity other than hydrogen, residual propylene is less than 0.1 volume
Ppm, methane are 0.3 volume ppm, ethane is 0.5 volume ppm, butane is 0.6 volume ppm.
[comparative example 1]
The rate that supports of catalyst based on carrier is set as 0.0005%, in addition to this in condition same as Example 1
Under, propane manufactured by the hydrogenation reaction to propylene.
Entrance 10a by the hydrogenation reaction to propylene in the reaction tower 10 under above-mentioned condition, in autoreaction tower 10
It rises and shows that maximum heating temperature is 220 DEG C at the position of distance 10cm.
By the gas chromatograph 17 of Shimadzu Corporation to the propane being discharged from the outlet 10b of reaction tower 10
Impurity contained by gas is analyzed, in the impurity other than hydrogen, residual propylene is 1.3 volume ppm, methane be 0.2 volume ppm,
Ethane is 0.3 volume ppm, butane less than 0.1 volume ppm.
[comparative example 2]
The rate that supports of catalyst based on carrier is set as 0.0005%, the height of reaction tower 10 is set as the 2 of embodiment 1
Times, the packed height in the reaction tower 10 for having supported the carrier of catalyst is set as 2 times of embodiment 1.In addition to this, with reality
It applies example 1 and propane has been manufactured by the hydrogenation reaction to propylene under the same conditions.
Entrance 10a by the hydrogenation reaction to propylene in the reaction tower 10 under above-mentioned condition, in autoreaction tower 10
It rises and shows that maximum heating temperature is 220 DEG C at the position of distance 9cm.
By the gas chromatograph 17 of Shimadzu Corporation to the propane being discharged from the outlet 10b of reaction tower 10
Impurity contained by gas is analyzed, in the impurity other than hydrogen, residual propylene is 1.2 volume ppm, methane be 0.1 volume ppm,
Ethane is 0.3 volume ppm, butane less than 0.1 volume ppm.
[comparative example 3]
The rate that supports of catalyst based on carrier is set as 0.01%, each carrier uses the carrier of gamma-alumina.Except this
In addition, propane has been manufactured by the hydrogenation reaction to propylene under the same conditions as example 1.
Entrance 10a by the hydrogenation reaction to propylene in the reaction tower 10 under above-mentioned condition, in autoreaction tower 10
It rises and shows that maximum heating temperature is 240 DEG C at the position of distance 7cm.
By the gas chromatograph 17 of Shimadzu Corporation to the propane being discharged from the outlet 10b of reaction tower 10
Impurity contained by gas is analyzed, and in the impurity other than hydrogen, residual propylene is 1.0 volumes less than 0.1 volume ppm, methane
Ppm, ethane are 0.9 volume ppm, butane is 1.0 volume ppm.
[comparative example 4]
The rate that supports of catalyst based on carrier is set as 0.5%, each carrier uses the carrier of gamma-alumina.Except this with
Outside, propane has been manufactured by the hydrogenation reaction to propylene under the same conditions as example 1.
Entrance 10a by the hydrogenation reaction to propylene in the reaction tower 10 under above-mentioned condition, in autoreaction tower 10
It rises and shows that maximum heating temperature is 400 DEG C at the position of distance 4cm.
By the gas chromatograph 17 of Shimadzu Corporation to the propane being discharged from the outlet 10b of reaction tower 10
Impurity contained by gas is analyzed, and in the impurity other than hydrogen, residual propylene is less than 0.1 volume ppm, methane less than 0.1 volume
Ppm, ethane are 1.6 volume ppm, butane is 1900 volume ppm.
[comparative example 5]
By a part in the granular filled in reaction tower 10 as the carrier for having supported catalyst.As carrier,
The carrier for the triumphant good Co. Ltd. system of NE that material is gamma-alumina, average grain diameter is 3mm is used.There is no catalyst-loaded grain
The alumina balls that the rest part of shape component is made using Ya Suwang Co., Ltd. (ア ズ ワ Application (strain)) of average grain diameter 3mm.Base
0.5% is set as in the rate that supports of the catalyst of carrier.The volume of whole carriers of catalyst and not catalyst-loaded is supported
The sum of the volume of whole granulars relative to the ratio of the volume for the whole carriers for having supported catalyst be 500 times.It will load
The carrier and not catalyst-loaded granular for having carried catalyst mix, and fill out in such a way that short transverse size reaches 50cm
It is charged in reaction tower 10.In addition to this, third has been manufactured by the hydrogenation reaction to propylene under the same conditions as example 1
Alkane.
Entrance 10a by the hydrogenation reaction to propylene in the reaction tower 10 under above-mentioned condition, in autoreaction tower 10
It rises and shows that maximum heating temperature is 50 DEG C at the position of distance 5cm.
By the gas chromatograph 17 of Shimadzu Corporation to the propane being discharged from the outlet 10b of reaction tower 10
Impurity contained by gas is analyzed, and in the impurity other than hydrogen, residual propylene is 30 volume %, methane is 1.3 volume ppm, second
Alkane is 0.4 volume ppm, butane is 0.5 volume ppm.
Analysis result in embodiment 1 and the Comparative Examples 1 to 5 is shown in table 1 below.
[table 1]
(embodiment 2)
The ethylene that purity is more than 99.99 volume % is supplied from olefin gas cylinder 2, in addition to this, same as Example 1
Under conditions of ethane manufactured by the hydrogenation reaction to ethylene.
Entrance 10a by the hydrogenation reaction to ethylene in the reaction tower 10 under above-mentioned condition, in autoreaction tower 10
It rises and shows that maximum heating temperature is 250 DEG C at the position of distance 6cm.
By the gas chromatograph 17 of Shimadzu Corporation to the ethane being discharged from the outlet 10b of reaction tower 10
Impurity contained by gas is analyzed, and in the impurity other than hydrogen, residual ethylene is 0.3 volume less than 0.1 volume ppm, methane
Ppm, propane are less than 0.1 volume ppm.
[comparative example 6]
The rate that supports of catalyst based on carrier is set as 0.0005%, in addition to this in condition same as Example 2
Under, ethane manufactured by the hydrogenation reaction to ethylene.
Entrance 10a by the hydrogenation reaction to ethylene in the reaction tower 10 under above-mentioned condition, in autoreaction tower 10
It rises and shows that maximum heating temperature is 240 DEG C at the position of distance 8cm.
By the gas chromatograph 17 of Shimadzu Corporation to the ethane being discharged from the outlet 10b of reaction tower 10
Impurity contained by gas is analyzed, in the impurity other than hydrogen, residual ethylene is 1.0 volume ppm, methane be 0.2 volume ppm,
Propane is less than 0.1 volume ppm.
[comparative example 7]
The rate that supports of catalyst based on carrier is set as 0.01%, each carrier uses the carrier of gamma-alumina.Except this
In addition, ethane has been manufactured by the hydrogenation reaction to ethylene under the same conditions as in practical example 2.
Entrance 10a by the hydrogenation reaction to ethylene in the reaction tower 10 under above-mentioned condition, in autoreaction tower 10
It rises and shows that maximum heating temperature is 260 DEG C at the position of distance 5cm.
By the gas chromatograph 17 of Shimadzu Corporation to the ethane being discharged from the outlet 10b of reaction tower 10
Impurity contained by gas is analyzed, and in the impurity other than hydrogen, residual ethylene is 1.0 volumes less than 0.1 volume ppm, methane
Ppm, propane are less than 0.1 volume ppm.
Analysis result in embodiment 2 and comparative example 6,7 is shown in table 2 below.
[table 2]
It can confirm from embodiment 1,2 and comparative example 1~7, by making metallic catalyst used in the hydrogenation reaction of alkene
Support rate less than 0.01%, the local pyrexia in reaction tower 10 can be reduced, impurity generated in side reaction can be made respectively
Concentration less than 1.0 volume ppm, be able to suppress impurity production quantity.0.0005% is set as rate will be supported furthermore, it is possible to confirm
In the case of, even if the packed height of the height of reaction tower 10 and the carrier for having supported catalyst is increased, can not be substantially reduced
Unreacted alkene can be substantially reduced unreacted alkene in contrast, being set as 0.001% by that will support rate.
According to above embodiment, by the weight for the catalyst for respectively supporting carrier relative to the respective weight of carrier
The ratio of the sum of the weight of catalyst respectively supported with carrier is set as less than 0.01%, even if not mixing without catalytic activity
Granular, also can be reduced reaction heat, excessive temperature caused by preventing due to local pyrexia rises, and is able to suppress because of alkene
Decomposition caused by impurity generate, can prevent impurity production quantity from generating uneven.In addition, by that can not need to be not used as carrier
Granular, can also prevent that local pyrexia, to prevent impurity production quantity from generating uneven.Pass through the catalyst for respectively supporting carrier
The sum of the weight of catalyst that is respectively supported relative to the respective weight of carrier and carrier of weight ratio be set as 0.001% with
On, it can make that the hydrogenation reaction of alkene definitely occurs, and it is manufactured that unreacted alkene can be prevented to be mixed into as impurity
Alkane in.In addition, by that granular all as the carrier for having supported catalyst, can be made to alkene plus hydrogen anti-
It should more precisely occur, unreacted alkene can be prevented to be mixed into manufactured alkane as impurity, and can be definitely
The catalyst distribution reduced in reaction tower 10 is uneven, can definitely prevent impurity production quantity from generating uneven.
The purity of the alkane manufactured by above embodiment is preferably more than 99.99 volume %, more preferably 99.999
Volume % or more.
The present invention is not limited to above embodiment and embodiments.
For example, can not make the granular filled in reaction tower 10 all as the load for having supported catalyst
Body, but make a part in the granular filled in reaction tower 10 as the carrier for having supported catalyst, and is not carried on a shoulder pole
The remainder of the granular of carried catalyst mixes.In this case, the catalyst that carrier respectively supports is relative to reaction tower 10
In the sum of the weight of catalyst that respectively supports of the respective weight of carrier and carrier ratio be 0.001% more than and less than
0.01%, and the total weight of the catalyst of whole supported carriers is granular relative to the whole comprising carrier in reaction tower 10
The ratio of the sum of the total weight of component and whole total weights of catalyst of supported carrier be 0.001% more than and less than
0.01%.That is, not only meeting 0.001≤wc×100/(ws+wc) < 0.01, and by reaction tower 10 as carrier
The total weight of granular is set as Σ ws, Σ w will be set as not as the total weight of the granular of carrierg, will be carried on a shoulder pole by whole carriers
The total weight of the catalyst of load is set as Σ wcWhen, also satisfaction 0.001≤Σ wc×100/(Σws+Σwg+Σwc).Whereby, full
0.001≤w of footc×100/(ws+wc) < 0.01 the present invention in, supported catalyst even if not being only filled in reaction tower 10
Carrier also ensure that catalytic amount in the case where also filling up not as carrier without catalyst-loaded granular, make pair
The hydrogenation reaction of alkene definitely occurs, and unreacted alkene is prevented to be mixed into manufactured alkane as impurity.In addition, because
For wc×100/(ws+wc) < 0.01, so Σ wc×100/(Σws+Σwg+Σwc) < 0.01.
In addition, the method that hydrogen is separated with the alkane that the reaction by alkene and hydrogen generates is not particularly limited.
For example, can be by the way that the alkane of the gas phase imported in products pot 15 be adsorbed in absorption by pressure swing adsorption method in adsorption tower
Agent is discharged using hydrogen as non-adsorbed gas from adsorption tower, thus in the case where not making the liquefied situation of alkane by hydrogen and alkane point
From improving the purity of alkane.
Symbol description
1 ... alkane manufacturing device, 2 ... olefin gas cylinders, 6 ... hydrogen cylinders, 10 ... reaction towers,
15 ... products pots.
Claims (6)
1. a kind of manufacturing method of alkane will to fill multiple granulars without catalytic activity into reaction tower
At least part in the granular passes through the catalyst in the reaction tower as the carrier for having supported catalyst
In the presence of gas phase state alkene and hydrogen reaction come the method that manufactures alkane, which is characterized in that
Make the total weight of the catalyst of whole supported carriers relative to whole grains comprising the carrier
The ratio of the total weight of shape component and the sum of whole total weight of the catalyst of the supported carrier is 0.001% or more
And less than 0.01%,
The weight for the catalyst for supporting the carrier respectively is each relative to the respective weight of the carrier and the carrier
The ratio of the sum of weight from the catalyst supported is 0.001% more than and less than 0.01%.
2. the manufacturing method of alkane as described in claim 1, which is characterized in that by the granular all as load
The carrier of the catalyst is carried.
3. the manufacturing method of alkane as described in claim 1, which is characterized in that make a part in the granular
For the carrier for having supported the catalyst, and it is mixed with the rest part for the granular for not supporting the catalyst
It closes.
4. the manufacturing method of alkane according to any one of claims 1 to 3, which is characterized in that the alkene be ethylene,
Propylene, n-butene or isobutene.
5. the manufacturing method of alkane as described in any one of claims 1 to 4, which is characterized in that the catalyst includes
Palladium, the carrier are aluminium oxide.
6. as alkane according to any one of claims 1 to 5 manufacturing method, which is characterized in that the alkane it is pure
Degree is more than 99.99 volume %.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-254666 | 2016-12-28 | ||
| JP2016254666A JP6251377B1 (en) | 2016-12-28 | 2016-12-28 | Paraffin production method |
| PCT/JP2017/041978 WO2018123363A1 (en) | 2016-12-28 | 2017-11-22 | Production method for paraffin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109843835A true CN109843835A (en) | 2019-06-04 |
| CN109843835B CN109843835B (en) | 2022-07-15 |
Family
ID=60685750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780063374.XA Active CN109843835B (en) | 2016-12-28 | 2017-11-22 | Process for producing paraffin |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6251377B1 (en) |
| KR (1) | KR102468527B1 (en) |
| CN (1) | CN109843835B (en) |
| TW (1) | TWI741077B (en) |
| WO (1) | WO2018123363A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103517891A (en) * | 2011-05-16 | 2014-01-15 | 纳幕尔杜邦公司 | Catalytic hydrogenation of fluoroolefins, alpha-alumina supported palladium compositions and their use as hydrogenation catalysts |
| JP2014084285A (en) * | 2012-10-22 | 2014-05-12 | Sumitomo Seika Chem Co Ltd | Process for producing paraffin |
| CN103804113A (en) * | 2012-11-06 | 2014-05-21 | 住友精化株式会社 | Method of producing paraffin and apparatus of producing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3509226A (en) | 1966-05-25 | 1970-04-28 | Exxon Research Engineering Co | Process for hydrogenating propylene |
| JP2684285B2 (en) * | 1991-12-13 | 1997-12-03 | 株式会社テイエルブイ | Decompression evaporative cooling equipment |
| JP5986477B2 (en) * | 2012-10-18 | 2016-09-06 | 住友精化株式会社 | Paraffin manufacturing method and manufacturing apparatus |
-
2016
- 2016-12-28 JP JP2016254666A patent/JP6251377B1/en active Active
-
2017
- 2017-11-22 KR KR1020197012389A patent/KR102468527B1/en active IP Right Grant
- 2017-11-22 WO PCT/JP2017/041978 patent/WO2018123363A1/en active Application Filing
- 2017-11-22 CN CN201780063374.XA patent/CN109843835B/en active Active
- 2017-11-23 TW TW106140683A patent/TWI741077B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103517891A (en) * | 2011-05-16 | 2014-01-15 | 纳幕尔杜邦公司 | Catalytic hydrogenation of fluoroolefins, alpha-alumina supported palladium compositions and their use as hydrogenation catalysts |
| JP2014084285A (en) * | 2012-10-22 | 2014-05-12 | Sumitomo Seika Chem Co Ltd | Process for producing paraffin |
| CN103804113A (en) * | 2012-11-06 | 2014-05-21 | 住友精化株式会社 | Method of producing paraffin and apparatus of producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20190100905A (en) | 2019-08-29 |
| KR102468527B1 (en) | 2022-11-17 |
| TWI741077B (en) | 2021-10-01 |
| CN109843835B (en) | 2022-07-15 |
| JP2018104380A (en) | 2018-07-05 |
| TW201835013A (en) | 2018-10-01 |
| JP6251377B1 (en) | 2017-12-20 |
| WO2018123363A1 (en) | 2018-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102285859B (en) | Selective hydrogenation process for C4 material flow with high concentration of butadiene | |
| JP4860688B2 (en) | Double bond hydroisomerization method | |
| CN104098425B (en) | A kind of C 2 fraction selective hydrogenation method | |
| KR102339192B1 (en) | Method for hydrogenating aromatic compounds | |
| JP2008536863A (en) | Improved double bond hydroisomerization process | |
| CN102285860B (en) | Selective hydrogenation process for C4 material flow with high concentration of alkyne | |
| CN106608805B (en) | A kind of method of liquid phase selective hydrogenation of C 3 hydrocarbons | |
| TW202100239A (en) | Gas replacement method and device, and hydrogenation method for nitro compound | |
| JP4148777B2 (en) | Method for hydrogenating liquid organic compounds | |
| CN102264688B (en) | Process for preparing bis(para-aminocyclohexyl)methane | |
| CN107089917A (en) | Multiple stage fluidized-bed middle nitrobenzene compounds Hydrogenation for amino benzenes compounds technique | |
| CN103342624A (en) | Preparation method of high purity cyclopentene | |
| CN109843835A (en) | The manufacturing method of alkane | |
| CN101274895A (en) | Hydrogenation reduction method for aromatic nitro compound | |
| KR102047139B1 (en) | Method and apparatus for producing paraffin | |
| CN103664457A (en) | Selective hydrogenation method of crude isopentene | |
| WO2016091058A1 (en) | Method for preparing 3-pentanone from 2-pentene | |
| CN105175213A (en) | Method for hydrogenation of C5 dicyclopentadiene | |
| US10800721B1 (en) | Method for preparing 2-Cyclohexyl cyclohexanol | |
| JP6034653B2 (en) | Paraffin production method | |
| CN105481627B (en) | A kind of high-purity propane production method for environmental protection refrigerant R290 | |
| CN107970927A (en) | Selective hydrogenation of pyrolysis gas catalyst, preparation method and method of hydrotreating | |
| WO2011136345A1 (en) | Process for producing methanol | |
| CN104211706B (en) | Method for synthesizing triethylene diamine by using ethanol | |
| CN111978141B (en) | Cracking mixed C 4 Material selective hydrogenation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |