CN105481627B - A kind of high-purity propane production method for environmental protection refrigerant R290 - Google Patents
A kind of high-purity propane production method for environmental protection refrigerant R290 Download PDFInfo
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- CN105481627B CN105481627B CN201510852738.5A CN201510852738A CN105481627B CN 105481627 B CN105481627 B CN 105481627B CN 201510852738 A CN201510852738 A CN 201510852738A CN 105481627 B CN105481627 B CN 105481627B
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- C07—ORGANIC CHEMISTRY
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- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
Abstract
The present invention provides a kind of high-purity propane production method for environmental protection refrigerant R290.The present invention obtains high-purity propane using low-purity propane as raw material, through technical process such as pretreatment of raw material, saturated hydrogenation, separation and purifications, this high-purity propane can be used as environmental protection refrigerant R290.The added value of low-purity propane is not only greatly improved in the present invention, but also technological process is simple, and plant investment is few, and low energy consumption.The present invention can be used for the production field of environmental protection refrigerant.
Description
Technical field
The present invention relates to a kind of high-purity propane production methods for environmental protection refrigerant R290.
Background technology
Propane derives from a wealth of sources, and casing-head gas, gas field condensed liquid etc. all include a certain amount of propane；In addition, propane is still refined oil
One of the byproduct of device and naphtha steam cracking ethylene unit.But produce propylene except part propane is used for dehydrogenation
Outside, most propane is used as oil liquefied gas fuel, and added value of product is low.
Propane not only can be used as industrial chemicals production propylene, itself be also efficient and environmentally friendly one of refrigerant.Currently,
Domestic most commonly used refrigerant is still R22 refrigerants, and main component is hydrochlorofluorocarsolvent (i.e. HCFC), since it is to ozone layer
Harm is big,《Montreal Protocol》Regulation accelerates to eliminate hydrochlorofluorocarsolvent, stops the use of HCFC to the year two thousand thirty.As transition
Solution, R22 is just gradually by the hydrogen fluorohydrocarbon class refrigerant replacement such as R410A and R407C.Although R410A and R407C are to ozone layer
Without influence, but the greenhouse effects that they are generated have been even more than R22.
It is compared with above-mentioned fluorinated refrigerant, propane refrigerant is zero to the destruction of ozone layer, global warming coefficient GWP
It is very low, it is one of ideal refrigerant.Grinding for refrigerant is produced based on propane, iso-butane etc. currently, carrying out both at home and abroad
Study carefully.
The propane of refrigerant grade is very high to purity requirement, generally higher than 99.96% (weight).And it can obtain currently on the market
The purified propylene oxide obtained is relatively low, and a certain amount of alkene and other impurities are all contained in generally about 90% (weight) left and right substantially.
CN201210023400.5 describes the preparation method of a kind of high-purity propane, iso-butane and normal butane, and the raw material of use is ether
Change and aromatisation after remaining mixing carbon four, then through hydrogenated processing, rectifying separation acquisition propane, iso-butane and normal butane.Wherein
The mass content of propane is more than 99.0%, and the mass content of iso-butane is more than 99.0%, and the mass content of normal butane is more than 98%.
Two kinds of hydrogenation catalysts are used in the method：Main hydrogenating catalyst and additional hydrogen catalyst, main hydrogenating catalyst are loaded on auxiliary
Hydrogenation catalyst upstream, two catalyst centre are detached using inert carrier.Main hydrogenating catalyst uses gama-alumina to carry
Body, it is at least five kinds of in loaded Cu, Zn, Zr, K, F, P and B element, active metal in Pt, Pd, Mo, Co, Ni element 2
Kind.Additional hydrogen catalyst uses anatase titanium dioxide TiO2 for carrier, and carrier auxiliary agent is selected from Zr, P, K, La, Ce, Pd, Ag, Au, Mn element
In at least five kinds of, 2 kinds in Pt, Pd, Mo, Co element of active metal.Hydroconversion condition is：Volume space velocity is 2.0-8.0h-1, inlet temperature is 180-360 DEG C, and hydrogen-oil ratio (mole) is 100-600.The purified propylene oxide that the method obtains is not high, although available
Make Chemical Manufacture raw material, but can not be used as refrigerant；In addition, the hydrogenation unit that the method uses is more complicated, filling two
Kind hydrogenation catalyst, it is of high cost；Hydrogenation reaction temperature is high, and energy consumption is big.
Invention content
The present invention relates to a kind of high-purity propane production methods for environmental protection refrigerant R290, mainly for conventional art
Middle purified propylene oxide is not high, can not be used as refrigerant and the problems such as production cost is high, provide a kind of new high-purity propane
Production method.
To achieve the above object, the technical solution adopted by the present invention is as follows：It is a kind of to be used for the high-purity of environmental protection refrigerant R290
Propane production method is spent, this method is using low-purity propane as raw material, through techniques such as pretreatment of raw material, saturated hydrogenation, refining spearations
Process obtains high-purity propane, including following key step：
(1) low concentration propane initially enters feed material preparation units, removes the sulphur for including in raw material, water impurity；
(2) enter hydrogenation reactor by pretreated raw material, alkene is hydrogenated saturation as alkane in raw material；
(3) hydrogenation products enter refining spearation unit, and separation obtains high-purity propane product.
In above-mentioned technical proposal, the propane content in low concentration propane feed is more than 80% (weight).
Propane content in high product purity propane is more than 99.96% (weight).
Feed material preparation units include at least a desulfurization reactor and a dewatering dryer, after pretreatment of raw material,
Total sulfur content in raw material is less than 1ppm (weight), and water is less than 10ppm (weight).
Hydrogenation reactor is fixed bed or trickle bed reactor, and reactor is built-in to be crammed and hydrogenation catalyst.
Catalyst carrier for hydrgenating is aluminium oxide or activated carbon, and active component is one or more mixed in platinum, palladium, rhodium, nickel
Object is closed, auxiliary agent is one or more mixtures in cobalt, molybdenum, rare earth metal；Active component accounts for 0.005-5% (weights in catalyst
Amount), auxiliary agent accounts for 0.002-2% (weight), remaining is carrier.
Loading catalyst protective agent simultaneously in hydrogenation reactor, catalyst protective agent are silica and alumina mixture,
And the ratio of silica and aluminium oxide is 0-5 (weight)；The filling ratio of catalyst and catalyst protective agent in hydrogenation reactor
For 2-6 (weight).
The reaction condition of hydrogenation reactor is：Inlet temperature is 40-80 DEG C, and inlet pressure (gauge pressure) is 1.5-2.5MPa,
Hydrogen-oil ratio (mole) is 10-300, and raw material liquid phase volume air speed is 0.1-5.0h-1。
Refining spearation unit includes at least 2 rectifying columns, for detaching component lighter than propane in reaction product and ratio third
The component of alkane weight；Rectifying column is packed tower, sieve-plate tower or valve tower.
It is compared with other high-purity propane production methods, present invention process flow is simple, only includes pretreatment of raw material, saturation
Add three units such as hydrogen and refining spearation；Raw material after pretreatment, adds hydrogen saturation unit without loading two or more catalyst,
Therefore plant investment is few, and production cost is low；In addition, the hydrogenation reaction temperature of the present invention is low, energy consumption is small；Finally, the present invention obtains
Purified propylene oxide be more than 99.96% (weight), can be used directly as refrigerant R290, be greatly improved propane add
Value.
Description of the drawings
Fig. 1 is present invention process general flow chart.
Fig. 1 numbers explanation：A, feed material preparation units；B, hydrogenation reactor；C takes off light knockout tower；D takes off weight knockout tower；
1, raw material；2, pretreated raw material；3, add hydrogen saturated products；4, light component；5, crude product；6, high product purity propane；7,
Heavy constituent.
In Fig. 1, enters feed material preparation units A from propane feed 1 out-of-bounds, raw material 2 is obtained after desulfurization, dehydration；
Raw material 2 enters back into hydrogenation reactor B, and with the help of hydrogenation catalyst, the unsaturation component such as alkene therein is saturated, and is obtained
To adding hydrogen saturated products 3；This adds hydrogen saturated products 3 by taking off light knockout tower C and de- weight knockout tower D, to obtain high-purity third respectively
Alkane product 6, while by-product includes the mixtures such as light component 4, heavy constituent 7.
Below by specific implementation mode, the present invention is described in further detail, illustrate technical scheme of the present invention and
Technique effect.
Specific implementation mode
In the present invention, if without special instruction, all embodiments and preferred embodiment mentioned in this article can be with
Intercombination forms new technical solution.
In the present invention, if without special instruction, all technical characteristics and preferred feature mentioned in this article can be mutual
Combination forms new technical solution.
【Embodiment 1】
Propane content is 86% (weight) in raw material 1, and ethane content is 1.0% (weight), and propylene content is 1.5% (weight
Amount), butane content is 5.5% (weight), and butene content is 5.0% (weight), isopentane content 1.0%.In addition, in raw material 1
Water content is 150ppm (weight), and sulfur content is 36ppm (weight).
Enter feed material preparation units according to flow raw material shown in Fig. 11, feed material preparation units include a desulphurization reaction
Device and a drier carry out desulfurization and dehydration, and water content is less than 5ppm (weight) after processing, and sulfur content is less than 1ppm (weights
Amount).
Hydrogenation reactor is fixed bed reactors, and the catalyst carrier for hydrgenating of filling is aluminium oxide, catalyst activity component
For palladium, auxiliary agent is cobalt, and concrete composition (weight) is palladium 2.5%, cobalt 0.5%, aluminium oxide 97%.Protective agent in hydrogenation reactor
It is the mixture of silica and aluminium oxide, the mass ratio of silica and aluminium oxide is 1.Catalyst reactor and protectant matter
Amount is than being 4.
Hydrogenation reactor inlet temperature is 50 DEG C, and inlet pressure is 2.0MPa (gauge pressure), and hydrogen-oil ratio (mole) is 200, into
Feed liquid body volume space velocity is 1.5h-1。
It is valve tower to take off light knockout tower C, and the number of plates is 60 pieces, reflux ratio 3.0.De- weight knockout tower D is valve tower, column plate
Number is 130 pieces, reflux ratio 5.0.
It is demonstrated experimentally that using the method for the present invention, the purity of product propane is 99.99% (weight).
【Embodiment 2】
Propane content is 93% (weight) in raw material 1, and ethane content is 0.5% (weight), and butane content is 2.5% (weight
Amount), butene content is 3.0% (weight), isopentane content 1.0%.In addition, water content is 500ppm (weight), sulphur in raw material 1
Content is 60ppm (weight).
Enter feed material preparation units according to flow raw material shown in Fig. 11, feed material preparation units include two desulphurization reactions
Device and two driers carry out desulfurization and dehydration, and water content is less than 10ppm (weight) after processing, and sulfur content is less than 1ppm (weights
Amount).
Hydrogenation reactor is fixed bed reactors, and the catalyst carrier for hydrgenating of filling is aluminium oxide, catalyst activity component
For nickel, auxiliary agent is molybdenum, and concrete composition (weight) is nickel 3.5%, molybdenum 0.1%, aluminium oxide 96.4%.Protection in hydrogenation reactor
Agent is the mixture of silica and aluminium oxide, and the mass ratio of silica and aluminium oxide is 1.Catalyst reactor and protectant
Mass ratio is 5.
Hydrogenation reactor inlet temperature is 80 DEG C, and inlet pressure is 1.8MPa (gauge pressure), and hydrogen-oil ratio (mole) is 280, into
Feed liquid body volume space velocity is 0.8h-1。
It is valve tower to take off light knockout tower C, and the number of plates is 50 pieces, reflux ratio 1.5.De- weight knockout tower D is valve tower, column plate
Number is 90 pieces, reflux ratio 3.0.
It is demonstrated experimentally that using the method for the present invention, the purity of product propane is 99.96% (weight).
【Embodiment 3】
Propane content is 96% (weight) in raw material 1, and ethane content is 0.1% (weight), and propylene content is 0.9% (weight
Amount), butane content is 1.5% (weight), and butene content is 1.0% (weight), isopentane content 0.5%.In addition, in raw material 1
Water content is 100ppm (weight), and sulfur content is 10ppm (weight).
Enter feed material preparation units according to flow raw material shown in Fig. 11, feed material preparation units include a desulphurization reaction
Device and two driers carry out desulfurization and dehydration, and water content is less than 5ppm (weight) after processing, and sulfur content is less than 1ppm (weights
Amount).
Hydrogenation reactor is trickle bed reactor, and the catalyst carrier for hydrgenating of filling is activated carbon, catalyst activity component
For platinum, auxiliary agent is cobalt, and concrete composition (weight) is platinum 0.5%, and cobalt 0.05%, remaining is activated carbon.Guarantor in hydrogenation reactor
Shield agent is the mixture of silica and aluminium oxide, and the mass ratio of silica and aluminium oxide is 3.Catalyst reactor and protective agent
Mass ratio be 2.
Hydrogenation reactor inlet temperature is 40 DEG C, and inlet pressure is 1.5MPa (gauge pressure), and hydrogen-oil ratio (mole) is 150, into
Feed liquid body volume space velocity is 2.2h-1。
It is packed tower to take off light knockout tower C, and packed height is 15 meters, reflux ratio 1.0.De- weight knockout tower D is packed tower, is filled out
Material height is 30 meters, reflux ratio 2.5.
It is demonstrated experimentally that using the method for the present invention, the purity of product propane is 99.97% (weight).
Claims (7)
1. a kind of high-purity propane production method for environmental protection refrigerant R290, it is characterised in that：This method is with low-purity third
Alkane is raw material, through pretreatment of raw material, saturated hydrogenation, refining spearation technical process, obtains high-purity propane, including following main step
Suddenly：
(1) low concentration propane weight percentage composition ＞ 80% is first passed around comprising desulfurization reactor, dewatering dryer equipment it is pre-
Processing unit, remove raw material in sulphur and water impurity, after pretreatment, in raw material the content of sulphur and water be respectively smaller than 1ppm and
10ppm；
(2) pass through hydrogenation reactor by pretreated raw material, the alkene in raw material is hydrogenated to saturated alkane, hydrogenation reactor
In catalyst activity component be platinum, palladium, rhodium, one or more mixtures in nickel, auxiliary agent is in cobalt, molybdenum, rare earth metal
One or more mixtures；The reaction condition of hydrogenation reactor is：Inlet temperature is 40-80 DEG C, inlet pressure 1.5-
2.5MPa, hydrogen/oil mol ratio 10-300, raw material liquid phase volume air speed are 0.1-5.0h-1；
(3) hydrogenation products enter refining spearation unit, and separation obtains high-purity propane product, and refining spearation unit includes at least two
A rectifying column, the high-purity propane product obtained after separation are refrigerant grade propane, propane weight percentage composition ＞ 99.96%.
2. a kind of high-purity propane production method for environmental protection refrigerant R290 according to claim 1, feature exist
Propane weight percentage composition in low concentration propane feed is more than 80%.
3. a kind of high-purity propane production method for environmental protection refrigerant R290 according to claim 1, feature exist
Propane weight percentage composition in high product purity propane is more than 99.96%.
4. a kind of high-purity propane production method for environmental protection refrigerant R290 according to claim 1, feature exist
A desulfurization reactor and a dewatering dryer are included at least in feed material preparation units.
5. a kind of high-purity propane production method for environmental protection refrigerant R290 according to claim 1, feature exist
In hydrogenation reactor be fixed bed or trickle bed reactor；Reactor is built-in to be crammed and hydrogenation catalyst；Catalyst carrier is oxygen
Change aluminium or activated carbon, active component is one or more mixtures in platinum, palladium, rhodium, nickel, and auxiliary agent is in cobalt, molybdenum, rare earth metal
One or more mixtures；Active component weight percentage accounts for 0.005-5% in catalyst, and auxiliary agent weight percentage accounts for
0.002-2%, remaining is carrier.
6. a kind of high-purity propane production method for environmental protection refrigerant R290 according to claim 1, feature exist
In in hydrogenation reactor simultaneously loading catalyst protective agent；Catalyst protective agent is silica and alumina mixture, and is aoxidized
The weight percentage ratio of silicon and aluminium oxide is 0-5；The charge weitght of catalyst and catalyst protective agent in hydrogenation reactor
Percentage composition ratio is 2-6.
7. a kind of high-purity propane production method for environmental protection refrigerant R290 according to claim 1, feature exist
2 rectifying columns are included at least in refining spearation unit, for detaching component lighter than propane in reaction product and than propane weight
Component；Rectifying column is packed tower, sieve-plate tower or valve tower.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1508103A (en) * | 2002-12-16 | 2004-06-30 | 中国石油化工股份有限公司 | Method for preparing alkane by hydrogenation of hydrocarbon raw material and catalyst used thereof |
| CN101244973A (en) * | 2007-02-15 | 2008-08-20 | 中国石油化工股份有限公司 | Method for removing alkyne in high purity isoprene |
| CN102633585A (en) * | 2012-02-03 | 2012-08-15 | 南京迈森科技发展有限公司 | Method for preparing high-purity propane, iso-butane and n-butane |
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- 2015-11-23 CN CN201510852738.5A patent/CN105481627B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1508103A (en) * | 2002-12-16 | 2004-06-30 | 中国石油化工股份有限公司 | Method for preparing alkane by hydrogenation of hydrocarbon raw material and catalyst used thereof |
| CN101244973A (en) * | 2007-02-15 | 2008-08-20 | 中国石油化工股份有限公司 | Method for removing alkyne in high purity isoprene |
| CN102633585A (en) * | 2012-02-03 | 2012-08-15 | 南京迈森科技发展有限公司 | Method for preparing high-purity propane, iso-butane and n-butane |
Non-Patent Citations (1)
| Title |
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| 从油田气中生产高纯度丙烷;邓天洲;《油田地面工程》;19840831;第3卷(第3期);第21-26页 * |
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Inventor after: Zhang Mao Inventor before: Xu Endong |
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Address after: 274000 Shandong Heze Development Zone Shanghai road and Danyang Road intersection 100 meters west. Applicant after: Shandong Yue an new material Co.,Ltd. Address before: 274000 Shandong Heze Development Zone Shanghai road and Danyang Road intersection 100 meters west. Applicant before: SHANDONG YUEON CHEMICAL CO.,LTD. |
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Denomination of invention: A High Purity Propane Production Method for Environmentally Friendly Refrigerant R290 Effective date of registration: 20230330 Granted publication date: 20180727 Pledgee: Heze rural commercial bank Limited by Share Ltd. Pledgor: Shandong Yue an new material Co.,Ltd. Registration number: Y2023980036490 |
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