CN108147939A - A kind of recovery method of cyclohexene hydrating process and its hydrogen containing tail gas - Google Patents
A kind of recovery method of cyclohexene hydrating process and its hydrogen containing tail gas Download PDFInfo
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- CN108147939A CN108147939A CN201810074250.8A CN201810074250A CN108147939A CN 108147939 A CN108147939 A CN 108147939A CN 201810074250 A CN201810074250 A CN 201810074250A CN 108147939 A CN108147939 A CN 108147939A
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- hydrogen
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- 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
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/048—Composition of the impurity the impurity being an organic compound
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of cyclohexene hydrating process and its recovery methods of hydrogen containing tail gas.The recovery method of hydrogen containing tail gas provided by the invention is that hydrogen containing tail gas declines pressure by flash distillation, cool removal condensate liquid；Then gas is adsorbed by porous adsorbent, the tail gas after absorption is to recycle product；The gas of the recovery method recycling gained of hydrogen containing tail gas directly feeds the low pressure benzene hydrogenation and device for producing hydrogen of cyclohexane oxidation legal system alcohol ketone, benzene hydrogen preheating gasifier, benzene vaporization superheater is sequentially entered together with benzene feedstock as hydrogen feed gas as described above；Hydrogen is heated, and benzene reacts after being gasified completely with cyclohexene for benzene hydrogenation device, generates hexamethylene.The present invention fully meets requirement of the cyclohexane oxidation legal system alcohol ketone to raw hydrogen precision so that is only reasonably comprehensively utilized as the hydrogen containing tail gas of torch gas burning and exhausting, reduces production and operation cost, improves the economic use value of hydrogen containing tail gas.
Description
Technical field
The present invention relates to the production fields of cyclohexanol, and in particular to time of a kind of cyclohexene hydrating process and its hydrogen containing tail gas
Receiving method.
Background technology
In the prior art, more advanced cyclohexene hydration method technique is generally taken in the production of cyclohexanol, and Japanese Asahi Chemical Industry is public
Department prepares cyclohexanol, and realize industrialization from 1990 realization cyclohexene hydration methods.And generating the required raw material of cyclohexene is
Cyclohexene, the production of cyclohexene are utilized under the action of hydrogenation catalyst, the partial hydrogenation generation cyclohexene of benzene selective, institute
Raw material is mainly benzene and hydrogen, and uneasiness is brought in production due to the limitation of hydrogenation catalyst and in view of hydrogen more than needed
Full hidden danger after cyclohexene is generated by partial hydrogenation of benzene, will pass through a flash system, and removing is dissolved in reaction oil phase
Hydrogen, reach and remove a hidden danger, but the hydrogen to flashing off but directly burns as torch gas, this is for production and operation
It is very uneconomic.Also, partial hydrogenation of benzene technique is larger to the consumption of hydrogen in itself, and impurity content is more complicated, hydrogen
It effectively recycles relatively difficult to achieve.
Invention content
The object of the present invention is to provide it is a kind of can to hydrogen carry out effectively recycling, recovery method simple possible one kind contain
The recovery method of hydrogen tail gas.
The present invention is achieved by the following technical solution：
A kind of recovery method of hydrogen containing tail gas includes step：
S1. hydrogen containing tail gas is after pressure is dropped to 0.5-0.55MPaG by flash distillation, and cool removal condensate liquid；
S2. and then gas is adsorbed by porous adsorbent, the tail gas after absorption is to recycle product
Further, in the recovery method of above-mentioned hydrogen containing tail gas, hydrogen containing tail gas material temperature is 120- in the step S1
140 DEG C, pressure 4-6MPaG.4-6MPaG, that is, gauge pressure 4-6MPa.
Further, in the recovery method of above-mentioned hydrogen containing tail gas, cooling to not higher than 20 DEG C in the step S1.
Further, in the recovery method of above-mentioned hydrogen containing tail gas, the porous adsorbent in the step S2 is activated carbon.
Further, in the recovery method of above-mentioned hydrogen containing tail gas, the porous adsorbent in the step S2 is supported on fixation
In bed adsorption plant, and the fixed bed adsorption equipment quantity is at least two sets.
The present invention also provides a kind of cyclohexene hydrating process：The recovery method recycling institute of hydrogen containing tail gas as described above
The gas obtained directly feeds the low pressure benzene hydrogenation and device for producing hydrogen of cyclohexane oxidation legal system alcohol ketone, with original as hydrogen feed gas
Material benzene sequentially enters benzene hydrogen preheating gasifier, benzene vaporization superheater together；Hydrogen is heated, after benzene is gasified completely with cyclohexene
It is reacted for benzene hydrogenation device, generates hexamethylene.
The recovery method of hydrogen containing tail gas provided by the invention has the advantages that：
The present invention fully meets requirement of the cyclohexane oxidation legal system alcohol ketone to raw hydrogen precision so that only as torch gas
The hydrogen containing tail gas of burning and exhausting is reasonably comprehensively utilized, and reduces production and operation cost, improves the economy of hydrogen containing tail gas
Utility value.
The present invention has huge economic value：Current 200,000 tons of the cyclohexene methods produce cyclohexanol project, contain per row beyond the highest heavens
Hydrogen tail gas burns about 1000m3/ h, institute's hydrogen is more than 95% in tail gas, is calculated by production run in 8000 hours, annual outer to arrange
About 8000000m3, often recycle 1m3Hydrogen converts into 1 yuan of calculating, and annual cost recovery can save at least 8,000,000 yuan.
In addition, by being adsorbed to the hydrogen containing tail gas, other organic gas are removed, make hydrogen purification, make hydrogen purity
Reach more than 99%, recycle again, the low pressure benzene hydrogenation of cyclohexane oxidation legal system alcohol ketone is directly fed as unstripped gas
With device for producing hydrogen, then enter benzene hydrogen preheating gasifier, benzene vaporization superheater together with benzene feedstock, hydrogen heated, benzene and hexamethylene
Alkene reacts after being gasified completely for benzene hydrogenation device, generates qualified hexamethylene, the raw material as downstream.
Specific embodiment
With reference to specific embodiment, the present invention will be further described.The embodiment is only the preferred implementation of the present invention
Example, is not intended to restrict the invention, for those skilled in the art, the present invention can have various changes and change
Change.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention
Protection domain within.Without percentage signified in the case of specified otherwise it is mass percent in each embodiment.
Embodiment 1
Hydrogenation reaction system is come out to the material for the hydrogen containing tail gas that pressure is 4-6MPaG, into a flash system, will be pressed
Power is down to 0.5-0.55MPaG, and the gas flow flashed off is 1001m3/ h, the gas analysis after flash distillation：Methane：It does not measure, it is organic
Gas：1.18%, hydrogen：98.82%；The gas flashed off enter device for cooling cool down to 18 DEG C hereinafter,
It will be above organic gas condensing more than dew point to get off recycling, the hydrogen containing micro organic gas enters adsorbent equipment, passes through work
Property charcoal carry out normal pressure absorption, be further adsorbed and removed micro organic gas, hydrogen be further purified.Gas after absorption
Body is analyzed：Methane：It does not measure, organic gas：0.21%, hydrogen：99.79%.Gas after absorption is sent into hydrogen gas buffer, pressure
Power is 0.5-0.55MPaG, and temperature≤50 DEG C are used as unstripped gas.
Embodiment 2
Hydrogenation reaction system is come out to the material for the hydrogen containing tail gas that pressure is 4-6MPaG, into a flash system, will be pressed
Power is down to 0.5-0.55MPaG, the gas flow flashed off be 1050m3/h, the gas analysis after flash distillation：Methane：It does not measure, it is organic
Gas：1.31%, hydrogen：98.69%；The gas flashed off enter device for cooling cool down to 18 DEG C hereinafter,
It will be above organic gas condensing more than dew point to get off recycling, the hydrogen containing micro organic gas enters adsorbent equipment, passes through work
Property charcoal carry out normal pressure absorption, be further adsorbed and removed micro organic gas, hydrogen be further purified.Gas after absorption
Body is analyzed：Methane：It does not measure, organic gas：0.26%, hydrogen：99.74%.Gas after absorption is sent into hydrogen gas buffer, pressure
Power is 0.5-0.55MPaG, and temperature≤50 DEG C are used as unstripped gas.
Embodiment 3
Hydrogenation reaction system is come out to the material for the hydrogen containing tail gas that pressure is 4-6MPaG, into a flash system, will be pressed
Power is down to 0.5-0.55MPaG, and the gas flow flashed off is 1105m3/ h, the gas analysis after flash distillation：Methane：It does not measure, it is organic
Gas：1.35%, hydrogen：98.65%；The gas flashed off enter device for cooling cool down to 18 DEG C hereinafter,
It will be above organic gas condensing more than dew point to get off recycling, the hydrogen containing micro organic gas enters adsorbent equipment, passes through work
Property charcoal carry out normal pressure absorption, be further adsorbed and removed micro organic gas, hydrogen be further purified.Gas after absorption
Body is analyzed：Methane：It does not measure, organic gas：0.26%, hydrogen：99.74%.Gas after absorption is sent into hydrogen gas buffer, pressure
Power is 0.5-0.55MPaG, and temperature≤50 DEG C are used as unstripped gas.
Embodiment 4
Hydrogenation reaction system is come out to the material for the hydrogen containing tail gas that pressure is 4-6MPaG, into a flash system, will be pressed
Power is down to 0.5-0.55MPaG, and the gas flow flashed off is 1116m3/ h, the gas analysis after flash distillation：Methane：It does not measure, it is organic
Gas：1.27%, hydrogen：98.73%；The gas flashed off enter device for cooling cool down to 18 DEG C hereinafter,
It will be above organic gas condensing more than dew point to get off recycling, the hydrogen containing micro organic gas enters adsorbent equipment, passes through work
Property charcoal carry out normal pressure absorption, be further adsorbed and removed micro organic gas, hydrogen be further purified.Gas after absorption
Body is analyzed：Methane：It does not measure, organic gas：0.20%, hydrogen：99.8%.Gas after absorption is sent into hydrogen gas buffer, pressure
Power is 0.5-0.55MPaG, and temperature≤50 DEG C are used as unstripped gas.
Unstripped gas obtained by embodiment 1 to embodiment 4 directly feeds the low pressure benzene hydrogenation of cyclohexane oxidation legal system alcohol ketone
With device for producing hydrogen, benzene hydrogen preheating gasifier, benzene vaporization superheater are sequentially entered together with benzene feedstock；
Hydrogen is heated, and benzene reacts after being gasified completely with cyclohexene for benzene hydrogenation device, generates hexamethylene.
Claims (6)
1. a kind of recovery method of hydrogen containing tail gas, which is characterized in that including step：
S1. hydrogen containing tail gas is after pressure is dropped to 0.5-0.55MPaG by flash distillation, and cool removal condensate liquid；
S2. and then gas is adsorbed by porous adsorbent, the tail gas after absorption is to recycle product.
2. the recovery method of hydrogen containing tail gas according to claim 1, which is characterized in that
Hydrogen containing tail gas material temperature is 120-140 DEG C in the step S1, pressure 4-6MPaG.
3. the recovery method of hydrogen containing tail gas according to claim 1, which is characterized in that
Cooling to not higher than 20 DEG C in the step S1.
4. the recovery method of hydrogen containing tail gas according to claim 1, which is characterized in that
Porous adsorbent in the step S2 is activated carbon.
5. the recovery method of hydrogen containing tail gas according to claim 1, which is characterized in that
Porous adsorbent in the step S2 is supported in fixed bed adsorption equipment, and the fixed bed adsorption equipment quantity is extremely
It is two sets less.
6. a kind of cyclohexene hydrating process, which is characterized in that including step：
According to the hydrogen containing tail gas as described in claim 1 to 5 recovery method recycling gained gas as hydrogen feed gas, directly
The low pressure benzene hydrogenation and device for producing hydrogen of supply cyclohexane oxidation legal system alcohol ketone are connect, the pre- hot gas of benzene hydrogen is sequentially entered together with benzene feedstock
Change device, benzene vaporization superheater；
Hydrogen is heated, and benzene reacts after being gasified completely with cyclohexene for benzene hydrogenation device, generates hexamethylene.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810074250.8A CN108147939A (en) | 2018-01-25 | 2018-01-25 | A kind of recovery method of cyclohexene hydrating process and its hydrogen containing tail gas |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810074250.8A CN108147939A (en) | 2018-01-25 | 2018-01-25 | A kind of recovery method of cyclohexene hydrating process and its hydrogen containing tail gas |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11322661A (en) * | 1998-05-11 | 1999-11-24 | Mitsubishi Chemical Corp | Production of cyclohexanone and production of epsilon-caprolactam |
| CN102180762A (en) * | 2011-03-23 | 2011-09-14 | 北京燕山集联石油化工有限公司 | Method for preparing cyclohexane |
| CN105688591A (en) * | 2016-01-26 | 2016-06-22 | 平顶山市神马万里化工股份有限公司 | Hydrogen-containing tail gas recycling process of cyclohexanol production device |
| CN205328609U (en) * | 2016-01-26 | 2016-06-22 | 平顶山市神马万里化工股份有限公司 | Hydrogeneous tail gas recycle system of cyclohexanol apparatus for producing |
-
2018
- 2018-01-25 CN CN201810074250.8A patent/CN108147939A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11322661A (en) * | 1998-05-11 | 1999-11-24 | Mitsubishi Chemical Corp | Production of cyclohexanone and production of epsilon-caprolactam |
| CN102180762A (en) * | 2011-03-23 | 2011-09-14 | 北京燕山集联石油化工有限公司 | Method for preparing cyclohexane |
| CN105688591A (en) * | 2016-01-26 | 2016-06-22 | 平顶山市神马万里化工股份有限公司 | Hydrogen-containing tail gas recycling process of cyclohexanol production device |
| CN205328609U (en) * | 2016-01-26 | 2016-06-22 | 平顶山市神马万里化工股份有限公司 | Hydrogeneous tail gas recycle system of cyclohexanol apparatus for producing |
Non-Patent Citations (2)
| Title |
|---|
| 上海市纺织工业局等: "《锦纶生产工艺》", 30 June 1977, 上海人民出版社 * |
| 崔克清等: "《化工工艺及安全》", 31 May 2004, 化学工业出版社 * |
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Application publication date: 20180612 |