CN106045810A - Isobutylene production method - Google Patents
Isobutylene production method Download PDFInfo
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- CN106045810A CN106045810A CN201610520344.4A CN201610520344A CN106045810A CN 106045810 A CN106045810 A CN 106045810A CN 201610520344 A CN201610520344 A CN 201610520344A CN 106045810 A CN106045810 A CN 106045810A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/11—Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/14875—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with organic compounds
- C07C7/14891—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with organic compounds alcohols
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Abstract
The invention relates to an isobutylene production method and mainly solves the problems of low isobutylene yield and high solvent consumption in the prior art. The isobutylene production method includes: using methanol as both an efficient absorbent to absorb-desorb, separate and remove light components below C3 in product gas and a raw material to be in MTBE (methyl tert-butyl ether) etherification reaction and cracking reaction with mixed carbon four containing isobutylene to obtain a high-purity isobutylene product. Therefore, purity of isobutylene is greater than or equal to 99.9%; once through yield of isobutylene is greater than or equal to 98.5%, consumption of methanol is less than or equal to 1.5%; the above problems are solved well, and the isobutylene production method can be applied in production for preparing isobutylene.
Description
Technical field
The present invention relates to a kind of isobutene. production method.
Background technology
Isobutene. is a kind of important industrial chemicals, is mainly used in synthesizing methyl tertbutyl ether (MTBE), it is also possible to be used for
Produce the elastomers such as butyl rubber, isoprene rubber, polyisoamylene rubber, it is also possible to be used for producing various fine chemicals.Along with
A large amount of productions of being continuously increased of the isobutene. downstream product market demand, especially MTBE, cause the demand of isobutene. to increase severely,
The contradiction of the global inadequate resource of isobutene., expands isobutene. source, increases isobutene. yield, becomes petrochemical industry development
An important topic.The important process route increasing isobutene. source is dehydrogenation of isobutane method.The method is with purity
Higher iso-butane is raw material, generates isobutene. product through catalytic dehydrogenating reaction.The separation process of isobutene. can be divided into removing C3
Light component and mixing C4 product purification two part below.The traditional method of the light component of removing below C3 is by supercharging and to use low
Temperature deep cooling rectificating method carry out separate obtain major product isobutene., but this separation method energy consumption is higher and equipment investment also
Higher.Mixing C4 product purification, currently mainly have sulphuric acid extraction, adsorption method of separation, iso-butane propylene cooxidation co-production method,
MTBE cracking process and n-butene isomerization process etc..Wherein: MTBE cracking process is a kind of advanced person and relatively inexpensive high purity
The method of isobutene., is also a kind of most widely used method of current high purity isobutene..The technical process of MTBE cracking process is
By mixing C 4 fraction under the catalytic action of storng-acid cation exchange resin, isobutene. and methanol are optionally etherified instead
Should generate MTBE, then MTBE is under catalytic action, and catalytic pyrolysis is isobutene. and methanol, prepares high-purity isobutylene product,
And methanol returns and recycles.
The method of number of patent application CN201210150386.5 iso-butane preparing isobutene of the prior art, discloses employing
It is 500～650 DEG C by iso-butane in reaction temperature, under the conditions of reaction pressure is 0.0～0.5MPa, by equipped with platinum group or chromium system
The reactor of dehydrogenation carries out dehydrogenation reaction, obtain comprising hydrogen, methane, ethylene, isobutene. and unconverted iso-butane and
The mixing logistics of heavy constituent, is compressed to 0.5～2.0MPa by this mixing logistics, carries out gas-liquid and divide under the conditions of being cooled to 5～60 DEG C
From, the liquid phase after separation, after absorbent absorption and separation and cut light tower, de-heavy oil column, obtains iso-butane and isobutyl
Alkene, isobutene. delivers to ether-based device, and iso-butane is recycled back into the technical scheme of dehydrogenation reactor system.Use hexane, hexamethylene,
Benzene,toluene,xylene, ethylbenzene, diethylene glycol ether, triethylene glycol ether, sulfolane, Aromatic raffinate etc. a kind of or combination containing 5
～18 carbon atom hydro carbons are as absorbent, reach hydrogen, methane and C2 fraction and separate with C3 fraction and above hydro carbons, point
From hydrogen purity high, equipment investment is low, and energy consumption is the lowest.
A number of patent application CN201110412796.8 absorption and separation preparing isobutene through dehydrogenation of iso-butane reactor product gas
System and method, discloses a kind of employing oil absorption process and replaces tradition rectificating method, to containing hydrogen, methane, carbon two, carbon
Three, the preparing isobutene through dehydrogenation of iso-butane reactor product gas of carbon four and a small amount of carbon five and more heavy constituent is effectively separated, and reduces different
Butylene loses, it is to avoid uses low temperature cold, not only reduces energy consumption but also can save equipment investment.Absorbent used is carbon five to carbon nine
A kind of or the mixture of the above component of two of which in component.
Number of patent application CN200980127847.3 contains, by cracking, the method that the mixture of MTBE prepares isobutene., open
Cracking MTBE raw material obtains product, under the pressure of 0.1MPa, by the division to product boiling spread, passes through
Rectification prepares the method for high-purity isobutylene.
The cracking of a number of patent application CN201310075610.3 methyl tertiary butyl ether(MTBE) prepare high-purity isobutene. system and
Method, discloses process system and includes: treating column；Reactor；Knockout drum；Methanol distillation column；Methanol water scrubber；Isobutene.
Lightness-removing column；Isobutene. weight-removing column；Described treating column, reactor, knockout drum, methanol water scrubber, isobutene. lightness-removing column and different
Butylene weight-removing column is sequentially connected with, and described knockout drum is connected with methanol distillation column, described methanol water scrubber and knockout drum
And methanol distillation column is formed and is connected in parallel.Meanwhile, the present invention also provides for one and utilizes described system by methyl tertbutyl ether-splitting
Solving the method preparing high-purity isobutene., described system and preparation method can produce the purity high-purity isobutene. more than 99.9%, and
The methanol of available more than 99% purity.
Number of patent application CN201520804219.7MTBE ether solution produces high-purity isobutene. equipment, and disclosing this equipment can make
Take highly purified isobutene., produce the once through yield of isobutene. up to 97～98%, methanol loss about 2%, the height produced
Purity isobutylene meets polymer grade requirement.
Number of patent application CN201210150386.5 of the prior art and number of patent application CN201110412796.8 takes off
Except the light component of below C3 uses absorption and separation method to be required to additionally to inject other high-boiling hydrocarbon as solvent, add solvent and deposit
The process stored up, reclaim, refine, this method not only operation energy consumption is higher, and equipment investment is the highest.Number of patent application
CN200980127847.3 is only Laboratory Production scale and pilot-plant production scale, there is large-scale industrial production and " puts
Big effect " problem.Number of patent application CN201310075610.3 and number of patent application CN201520804219.7 only with
MTBE is as the method for waste high-purity isobutylene product, and isobutene. yield is relatively low, solvent loss is bigger.
Thus, there is energy in the light component of below the removing C3 during prior art produces isobutene. and mixing C4 product purification method
The problems such as consumption is high, investment is big, isobutene. yield is low, solvent loss is big.
Summary of the invention
The technical problem to be solved is the problem that in prior art, safety is poor, it is provided that a kind of new isobutyl
Alkene production method.The method has the preferable advantage of safety.
For solving the problems referred to above, the technical solution used in the present invention is as follows: a kind of isobutene. production method, dehydrogenation of isobutane
The product gas including isobutene. that reaction is formed, is separated by the method comprised the steps:
(1) the light component of removing below C3: use methanol to carry out absorption and separation as high-efficiency absorbent, remove in reaction gas
Hydrogen, methane and lighter hydrocarbons, obtain the mixing C-4-fraction of rich isobutene.；Idiographic flow is: described product gas is at separation removal water
Rear entrance compressor, the gas that do not coagulates after overcompression cools down enters absorption tower tower reactor, and gas passes through absorption tower from below to up, with
The absorbent methanol counter current contacting entered from tower top, other hydro carbons beyond dehydrogenation gas, C1～C2 lighter hydrocarbons is inhaled by methanol absorbing agent
Receiving, the absorbent absorbing C3 and more than C3 hydro carbons is discharged from absorption tower tower reactor, after poor rich liquid heat exchanger heat exchange, enters molten
Agent recovery tower；Separate through rectification in solvent recovery tower rich in the absorbent of C3 and more than C3 hydro carbons, tower top separate C3～
C4 hydro carbons, enters lightness-removing column；The fixed gas that solvent recovery column overhead distillates returns to suction port of compressor, re-compresses recovery fixed gas
In C1～C2 and C3～C4；Solvent recovery tower tower reactor flows out the lean solution absorbent without C3 and more than C3 hydro carbons and fresh methanol
Mixing, after lean rich solution heat exchange, returns to top, absorption tower and recycles；C3～the C4 distillation of solvent recovery tower overhead condensation
Enter lightness-removing column together with the liquid phase hydro carbons of compressor outlet to carry out rectification and separate, isolate C3 fraction at tower top, obtain in tower reactor
Mixing C 4 fraction after removing hydrogen, C3 and below C3 lighter hydrocarbons；
(2) mixing C4 product purification: use methanol to carry out MTBE ether as raw material with the mixing C-4-fraction containing isobutene.
Change reaction and cracking reaction, it is achieved isobutene. and the separation of C4 isomer, obtain high-purity isobutylene product；Idiographic flow is:
Mixing C 4 fraction containing isobutene. enters MTBE methyltertiarvbutyl ether reactor together with excessive methanol, under catalyst action, isobutene. with
Methanol generation etherification reaction generates MTBE；The reactant of MTBE methyltertiarvbutyl ether reactor enters reactive distillation column, sets in reactive distillation column
There are catalyst, unreacted isobutene. and methanol to continue etherification reaction in reactive distillation column reaction bed and generate MTBE；Reaction
Rectifying column overhead enters deisobutanizer and carries out rectification separation, and obtains iso-butane at tower top, and iso-butane returns dehydrogenation
Reactor continues dehydrogenation reaction；Deisobutanizer tower reactor obtains the component including normal butane, 1-butylene；Reactive distillation column tower reactor obtains
The MTBE arrived enters MTBE cracking reactor, cracking reaction occurs under catalyst action, resolves into isobutene. and methanol；MTBE
Cracking reactor product enters water scrubber tower reactor, in water scrubber, and the water counter current contacting that isobutene. and methanol enter with tower top, first
Alcohol is discharged from water scrubber tower reactor after being only absorbed by the water, and enters methanol distillation column；Separate through methanol distillation column rectification, Methanol Recovery
The recovery methanol that tower tower reactor flows out mixes with fresh methanol, returns MTBE methyltertiarvbutyl ether reactor and continues reaction；Water scrubber tower top distillates
Thing enters essence isobutene. tower rectification and separates, and obtains high-purity isobutylene product at tower top, and tower reactor obtains MTBE, and the tert-butyl alcohol produces
Product.
In technique scheme, it is preferable that the operating condition on absorption tower is: operation gauge pressure 0.88～1.22MPa, operation temperature
Spend 50～70 DEG C.
In technique scheme, it is preferable that the operating condition of solvent recovery tower is operation gauge pressure 0.72～1.14MPa, behaviour
Make temperature 70～140 DEG C.
In technique scheme, it is preferable that the operating condition of lightness-removing column is: operation gauge pressure 1.86～2.34MPa, operation temperature
Spend 65～145 DEG C.
In technique scheme, it is preferable that the operating condition of MTBE methyltertiarvbutyl ether reactor is: use fixed bed reactors structure
Pattern, catalyst uses macropore strong acid cation exchanger resin, operates gauge pressure 0.68～0.72MPa, operates temperature 45～65
DEG C, material molar ratio is, mixes carbon four: methanol=1:0.42～0.58, and liquid charging stock air speed is 1.1～1.4 hours-1。
In technique scheme, it is preferable that the operating condition of reactive distillation column reaction bed is: catalyst uses macropore strong
Acid cation exchange resin, operates gauge pressure 0.58～0.66MPa, operation temperature 55～95 DEG C, reflux ratio 0.8～1.0.
In technique scheme, it is preferable that the operating condition of deisobutanizer is: operation gauge pressure 0.54～0.78MPa, behaviour
Make temperature 44～86 DEG C.
In technique scheme, it is preferable that the operating condition of MTBE cracking reactor is: use fixed bed reactors structure
Pattern, catalyst uses RKS02 solid acid, operates gauge pressure 0.52～0.68MPa, operation temperature 185～205 DEG C, MTBE raw material
Air speed is 2.5～3.5 hours-1。
In technique scheme, it is preferable that the operating condition of water scrubber is: operation gauge pressure 0.52～0.64MPa, operation temperature
Spend 46～82 DEG C.
In technique scheme, it is preferable that the operating condition of methanol distillation column is: operation gauge pressure 0.02～0.06MPa, behaviour
Make temperature 64～88 DEG C；The operating condition of essence isobutene. tower is: operation gauge pressure 0.46～0.66MPa, operation temperature 45～75 DEG C.
The present invention relates to the isobutene. production method of a kind of optimization, use methanol to carry out absorbing-solving as high-efficiency absorbent
Inhale and separate, the light component of below C3 in removing product gas；Methanol is used to enter with the mixing C-4-fraction containing isobutene. as raw material
Row MTBE etherification reaction and cracking reaction, separate isobutene. and C4 isomer, obtain high-purity isobutylene product.By
This, isobutene. product purity >=99.9%, isobutene. once through yield >=98.5%, methanol loss≤1.5%, achieve preferably
Technique effect.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the method for the invention.
In Fig. 1,1-gun barrel, 2-compressor, 3-absorption tower, 4-poor rich liquid heat exchanger, 5-solvent recovery tower, 6-takes off
Light tower, 7-MTBE methyltertiarvbutyl ether reactor, 8-reactive distillation column, 9-deisobutanizer, 10-MTBE cracking reactor, 11-water scrubber,
12-essence isobutene. tower, 13-methanol distillation column, 21-dehydrogenation of isobutane reactor product gas, 22-condensed water, reacts after 23-dehydration
Gas, 24-compression condensation liquid, product gas after 25-compression, 26-H2, C1～C2 lighter hydrocarbons, 27-contains C3 and above hydro carbons rich solution, 28-
Without C3 and above hydro carbons lean solution, 29-C1～C2 and C3～C4 fixed gas, 30-solvent recovery tower overhead, 31-C3 evaporates
Point, the dehydrogenation of isobutane reactor product C 4 fraction after 32-removing lighter hydrocarbons, 33-MTBE reaction supplements fresh methanol, and 34-circulation is molten
Agent supplements fresh methanol, 35-fresh methanol, 36-MTBE etherification reaction product, and 37-reactive distillation column overhead, 38-is just
Butane, 1-butylene, 39-iso-butane, 40-reactive distillation column tower bottoms, 41-MTBE cracking reactor product, 42-water scrubber tower top
Distillation, 43-isobutene. product, 44-MTBE, TBA product, 45-water scrubber tower bottoms, 46-methanol distillation column overhead,
47-fresh water, 48-reclaims recycle methanol.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Detailed description of the invention
[comparative example 1]
As a example by 100,000 tons/year of preparing isobutene through dehydrogenation of iso-butane devices, the composition of reaction gas is as follows:
| Composition, wt% | |
| Hydrogen | 2.90 |
| Methane | 0.80 |
| Ethylene | 0.30 |
| Ethane | 0.30 |
| Propylene | 0.40 |
| Propane | 1.20 |
| Normal butane | 1.00 |
| Iso-butane | 53.90 |
| N-butene | 0.90 |
| Isobutene. | 38.30 |
| Add up to | 100.00 |
In prior art, first iso-butane carries out catalytic dehydrogenating reaction, then enters after the contracting of dehydrogenation reaction product air pressure and inhales
Receiving tower, heavy constituent is entered desorber by solvent absorption, the rich hydrocarbon solvent absorbing a large amount of hydro carbons, and desorber overhead enters
Lightness-removing column, tower top isolates C3 fraction, and tower reactor obtains the C 4 reaction product gas after removing lighter hydrocarbons；Mixing carbon containing isobutene.
Four fractions carry out MTBE etherification reaction and cracking reaction again, it is achieved isobutene. and the separation of C4 isomer, finally obtain high-purity
Isobutene. product isobutene. product purity >=99.9%, isobutene. once through yield 97～98%, methanol loss is about 2%.
[embodiment 1]
In flow process as shown in Figure 1, including following 3 parts:
(1) the light component of removing below C3: use methanol to carry out absorption and separation as high-efficiency absorbent, by isobutene. product gas
Remove hydrogen, methane and the lighter hydrocarbons etc. in reaction gas through operations such as overcompression boosting, absorption-desorbing, rectification are de-light, obtain Fu Yi
The mixing C-4-fraction of butylene；
(2) mixing C4 product purification: the isobutene. in dehydrogenation of isobutane product mixing C-4-fraction and 1-butylene boiling
Point is the most close, uses methanol to carry out MTBE etherification reaction as raw material and the mixing C-4-fraction containing isobutene. and cracking is anti-
Should, it is achieved isobutene. and the separation of C4 isomer, obtain high-purity isobutylene product；
(3) methanol is both as high-efficiency absorbent, again as etherification reaction raw material, it is only necessary to a set of methanol recovery system, carries
The high utilization rate of methanol.Absorption and separation need not additionally inject other high-boiling hydrocarbon and makees solvent, it is to avoid newly-built a set of other
The system that solvent stores, reclaims, refines；Etherification reaction raw material only contains mixing C-4-fraction and the methanol of isobutene., does not has it
The probability that its high boiling hydrocarbon kind solvent is scurried into, adds the reliability of etherification reaction.
Removing below C3 light component stream journey is as follows: dehydrogenation of isobutane reaction generates the product gas such as isobutene. at separation removal water
Rear entrance compressor boost, is condensed through overcompression cooling rear portion hydro carbons, does not coagulates gas and enter absorption tower tower reactor.Gas from
Lower and on by absorption tower, and the absorbent methanol counter current contacting entered from tower top, other beyond dehydrogenation gas, C1～C2 lighter hydrocarbons
Hydro carbons is absorbed by methanol absorbing agent.The absorbent absorbing a large amount of C3 and above hydro carbons is discharged from absorption tower tower reactor, through rich or poor
After liquid heat exchanger heat exchange, enter solvent recovery tower.Rich in the absorbent of C3 and above hydro carbons in solvent recovery tower through rectification
Separate, separate C3～C4 hydro carbons at tower top, enter lightness-removing column.The fixed gas that solvent recovery column overhead distillates returns compressor and enters
Mouthful, re-compress C1～C2 and C3～C4 reclaimed in fixed gas.Solvent recovery tower tower reactor flows out without C3 and above hydro carbons
Lean solution absorbent mixes with fresh methanol, after lean rich solution heat exchange, returns to top, absorption tower and recycles.Solvent recovery tower tower
The distillation of top condensation enters lightness-removing column together with the liquid phase hydro carbons of compressor outlet to carry out rectification and separates, and isolates C3 at tower top
Fraction, obtains the mixing C 4 fraction after removing hydrogen, lighter hydrocarbons in tower reactor.
Mixing C4 product purification flow process is as follows: the mixing C 4 fraction containing isobutene. enters MTBE etherificate together with excessive methanol
Reactor, under catalyst action, isobutene. generates MTBE with methanol generation etherification reaction.Reactant enters reactive distillation column,
It is also provided with catalyst, unreacted isobutene. and methanol in reactive distillation column and in reactive distillation column reaction bed, continues etherificate instead
MTBE should be generated.Reactive distillation column overhead enters deisobutanizer and carries out rectification separation, and obtains iso-butane at tower top,
Iso-butane returns dehydrogenation reactor and continues dehydrogenation reaction.Deisobutanizer tower reactor obtains the component such as normal butane, 1-butylene.Reaction essence
Evaporate the MTBE entrance MTBE cracking reactor that tower tower reactor obtains, cracking reaction occurs under catalyst action, resolves into isobutene.
And methanol.MTBE cracking reactor product enters water scrubber tower reactor.In water scrubber, isobutene. and methanol and tower top entrance
Water counter current contacting, methanol is discharged from water scrubber tower reactor after being only absorbed by the water, and is entered methanol distillation column.Through methanol distillation column rectification
Separating, the recovery methanol that methanol distillation column tower reactor flows out mixes with fresh methanol, returns MTBE methyltertiarvbutyl ether reactor and continues reaction.Water
Washing column overhead distillation and enter essence isobutene. tower rectification separation, and obtain high-purity isobutylene product at tower top, tower reactor obtains
MTBE, the tert-butyl alcohol (TBA) product.
Still as a example by 100,000 tons/year of preparing isobutene through dehydrogenation of iso-butane devices, the composition of reaction gas, with comparative example 1.Use this
Invention methanol carries out absorbing-Desorption separation as high-efficiency absorbent, the light component of below C3 in removing product gas；Employing methanol is made
Carry out MTBE etherification reaction and cracking reaction for raw material with the mixing C-4-fraction containing isobutene., isobutene. and C4 isomer are entered
Row separates, and obtains high-purity isobutylene product.Absorption tower: operation gauge pressure 0.96MPa, operation temperature 54～68 DEG C.Solvent recovery
Tower: operation gauge pressure 1.08MPa, operation temperature 72～134 DEG C.Lightness-removing column: operation gauge pressure 2.02MPa, operates temperature 69～131
℃.MTBE methyltertiarvbutyl ether reactor: use fixed bed reactors structural shape, catalyst uses macropore strong acid cation exchange tree
Fat, operates gauge pressure 0.69MPa, operates temperature 62 DEG C, and material molar ratio is: mixing carbon four: methanol=1:0.48, and liquid charging stock is empty
Speed is 1.2 hours-1.Reactive distillation column reaction bed: catalyst uses macropore strong acid cation exchanger resin, operates gauge pressure
0.62MPa, operation temperature 57～91 DEG C, reflux ratio 0.9.Deisobutanizer: operation gauge pressure 0.68MPa, operates temperature 48～82
℃.MTBE cracking reactor: use fixed bed reactors structural shape, catalyst uses RKS02 solid acid, operates gauge pressure
0.59MPa, operates temperature 195 DEG C, and MTBE feed space velocity is 2.9 hours-1.Water scrubber: operation gauge pressure 0.58MPa, operates temperature
48～76 DEG C.Methanol distillation column: operation gauge pressure 0.04MPa, operation temperature 66～84 DEG C；Essence isobutene. tower: operation gauge pressure
0.58MPa, operation temperature 49～72 DEG C.Thus, isobutene. product purity >=99.9%, isobutene. once through yield 98.6%, first
Alcohol loss 1.5%.
[embodiment 2]
According to the condition described in embodiment 1 and step, still as a example by 100,000 tons/year of preparing isobutene through dehydrogenation of iso-butane devices,
Simply changing reaction gas composition, the composition of reaction gas is as follows:
Using methanol of the present invention to carry out absorbing-Desorption separation as high-efficiency absorbent, below the C3 in removing product gas is light
Component；Methanol is used to carry out MTBE etherification reaction and cracking reaction, by different as raw material with the mixing C-4-fraction containing isobutene.
Butylene and C4 isomer separate, and obtain high-purity isobutylene product.Absorption tower: operation gauge pressure 1.04MPa, operates temperature 58
～69 DEG C.Solvent recovery tower: operation gauge pressure 0.96MPa, operation temperature 71～120 DEG C.Lightness-removing column: operation gauge pressure 1.95MPa, behaviour
Make temperature 66～125 DEG C.MTBE methyltertiarvbutyl ether reactor: use fixed bed reactors structural shape, catalyst uses macropore strong acid
Cation exchange resin, operates gauge pressure 0.71MPa, operates temperature 64 DEG C, and material molar ratio is: mixing carbon four: methanol=1:
0.52, liquid charging stock air speed is 1.3 hours-1.Reactive distillation column reaction bed: catalyst uses macropore strong acid cation exchange
Resin, operates gauge pressure 0.64MPa, operation temperature 59～94 DEG C, reflux ratio 0.9.Deisobutanizer: operation gauge pressure 0.62MPa, behaviour
Make temperature 46～78 DEG C.MTBE cracking reactor: use fixed bed reactors structural shape, catalyst uses RKS02 solid acid,
Operation gauge pressure 0.62MPa, operates temperature 200 DEG C, and MTBE feed space velocity is 3.3 hours-1.Water scrubber: operation gauge pressure 0.62MPa,
Operation temperature 50～80 DEG C.Methanol distillation column: operation gauge pressure 0.05MPa, operation temperature 69～86 DEG C；Essence isobutene. tower: operation
Gauge pressure 0.62MPa, operation temperature 52～74 DEG C.Thus, isobutene. product purity >=99.9%, isobutene. once through yield
98.5%, methanol loss 1.4%.
[embodiment 3]
Form according to the condition described in embodiment 1 and step and reaction gas, use methanol of the present invention as efficient absorption
Agent carries out absorbing-Desorption separation, the light component of below C3 in removing product gas；Use methanol as raw material and mixing containing isobutene.
Close C-4-fraction and carry out MTBE etherification reaction and cracking reaction, isobutene. and C4 isomer are separated, obtains high-purity different
Butylene product.Simply production scale changes into 200,000 tons/year of preparing isobutene through dehydrogenation of iso-butane devices, and process condition also changes
Become.Absorption tower: operation gauge pressure 0.88MPa, operation temperature 50～64 DEG C.Solvent recovery tower: operation gauge pressure 0.72MPa, operation temperature
Spend 70～117 DEG C.Lightness-removing column: operation gauge pressure 1.86MPa, operation temperature 65～120 DEG C.MTBE methyltertiarvbutyl ether reactor: use fixing
Bed structure of reactor pattern, catalyst uses macropore strong acid cation exchanger resin, operates gauge pressure 0.68MPa, operates temperature
45 DEG C, material molar ratio is, mixes carbon four: methanol=1:0.42, liquid charging stock air speed is 1.1 hours-1.Reactive distillation column reacts
Bed: catalyst uses macropore strong acid cation exchanger resin, operates gauge pressure 0.58MPa, operation temperature 55～94 DEG C, backflow
Ratio 0.8.Deisobutanizer: operation gauge pressure 0.54MPa, operation temperature 44～73 DEG C.MTBE cracking reactor: use fixed bed
Structure of reactor pattern, catalyst uses RKS02 solid acid, operates gauge pressure 0.52MPa, operates temperature 185 DEG C, and MTBE raw material is empty
Speed is 2.5 hours-1.Water scrubber: operation gauge pressure 0.52MPa, operation temperature 46～76 DEG C.Methanol distillation column: operation gauge pressure
0.02MPa, operation temperature 64～82 DEG C；Essence isobutene. tower: operation gauge pressure 0.46MPa, operation temperature 45～70 DEG C.Thus, different
Butylene product purity >=99.9%, isobutene. once through yield 98.5%, methanol loss 1.5%.
[embodiment 4]
Form according to the condition described in embodiment 2 and step and reaction gas, use methanol of the present invention as efficient absorption
Agent carries out absorbing-Desorption separation, the light component of below C3 in removing product gas；Use methanol as raw material and mixing containing isobutene.
Close C-4-fraction and carry out MTBE etherification reaction and cracking reaction, isobutene. and C4 isomer are separated, obtains high-purity different
Butylene product.Simply production scale changes into 200,000 tons/year of preparing isobutene through dehydrogenation of iso-butane devices, and process condition also changes
Become.Absorption tower: operation gauge pressure 1.22MPa, operation temperature 55～70 DEG C.Solvent recovery tower: operation gauge pressure 1.14MPa, operation temperature
Spend 82～140 DEG C.Lightness-removing column: operation gauge pressure 2.34MPa, operation temperature 82～145 DEG C.MTBE methyltertiarvbutyl ether reactor: use fixing
Bed structure of reactor pattern, catalyst uses macropore strong acid cation exchanger resin, operates gauge pressure 0.72MPa, operates temperature
65 DEG C, material molar ratio is: mixing carbon four: methanol=1:0.58, liquid charging stock air speed is 1.4 hours-1.Reactive distillation column reacts
Bed: catalyst uses macropore strong acid cation exchanger resin, operates gauge pressure 0.66MPa, operation temperature 59～95 DEG C, backflow
Ratio 1.0.Deisobutanizer: operation gauge pressure 0.78MPa, operation temperature 55～86 DEG C.MTBE cracking reactor: use fixed bed anti-
Answering device structural shape, catalyst uses RKS02 solid acid, operates gauge pressure 0.68MPa, operates temperature 205 DEG C, MTBE feed space velocity
It it is 3.5 hours-1.Water scrubber: operation gauge pressure 0.64MPa, operation temperature 53～82 DEG C.Methanol distillation column: operation gauge pressure
0.06MPa, operation temperature 69～88 DEG C；Essence isobutene. tower: operation gauge pressure 0.66MPa, operation temperature 56～75 DEG C.Thus, different
Butylene product purity >=99.9%, isobutene. once through yield 98.5%, methanol loss 1.5%.
Claims (10)
1. an isobutene. production method, the product gas including isobutene. that dehydrogenation of isobutane reaction is formed, as follows by including
The method of step separates:
(1) the light component of removing below C3: use methanol to carry out absorption and separation as high-efficiency absorbent, remove the hydrogen in reaction gas
Gas, methane and lighter hydrocarbons, obtain the mixing C-4-fraction of rich isobutene.；Idiographic flow is: described product gas is after separation removal water
Entering compressor, the gas that do not coagulates after overcompression cools down enters absorption tower tower reactor, gas from below to up by absorption tower, with from
The absorbent methanol counter current contacting that tower top enters, other hydro carbons beyond dehydrogenation gas, C1～C2 lighter hydrocarbons is absorbed by methanol absorbing agent,
The absorbent absorbing C3 and more than C3 hydro carbons is discharged from absorption tower tower reactor, after poor rich liquid heat exchanger heat exchange, enters solvent
Recovery tower；Absorbent rich in C3 and more than C3 hydro carbons separates through rectification in solvent recovery tower, separates C3～C4 at tower top
Hydro carbons, enters lightness-removing column；The fixed gas that solvent recovery column overhead distillates returns to suction port of compressor, re-compresses in recovery fixed gas
C1～C2 and C3～C4；The lean solution absorbent that solvent recovery tower tower reactor flows out without C3 and more than C3 hydro carbons mixes with fresh methanol
Close, after lean rich solution heat exchange, return to top, absorption tower and recycle；C3～the C4 distillation of solvent recovery tower overhead condensation with
The liquid phase hydro carbons of compressor outlet enters lightness-removing column together and carries out rectification separation, isolates C3 fraction at tower top, obtains in tower reactor
Mixing C 4 fraction after removing hydrogen, C3 and below C3 lighter hydrocarbons；
(2) mixing C4 product purification: use methanol to carry out MTBE etherificate as raw material and the mixing C-4-fraction containing isobutene. anti-
Should and cracking reaction, it is achieved isobutene. and the separation of C4 isomer, obtain high-purity isobutylene product.Idiographic flow is: containing different
The mixing C 4 fraction of butylene enters MTBE methyltertiarvbutyl ether reactor together with excessive methanol, under catalyst action, and isobutene. and methanol
Etherification reaction is occurred to generate MTBE；The reactant of MTBE methyltertiarvbutyl ether reactor enters reactive distillation column, is provided with and urges in reactive distillation column
Agent, unreacted isobutene. and methanol continue etherification reaction in reactive distillation column reaction bed and generate MTBE；Reactive distillation
Column overhead distillation enters deisobutanizer and carries out rectification separation, and obtains iso-butane at tower top, and iso-butane returns dehydrogenation reaction
Device continues dehydrogenation reaction；Deisobutanizer tower reactor obtains the component including normal butane, 1-butylene；Reactive distillation column tower reactor obtains
MTBE enters MTBE cracking reactor, cracking reaction occurs under catalyst action, resolves into isobutene. and methanol；MTBE cracks
Reactor product enters water scrubber tower reactor, in water scrubber, and the water counter current contacting that isobutene. and methanol enter with tower top, methanol quilt
Water is discharged from water scrubber tower reactor after absorbing, and enters methanol distillation column；Separate through methanol distillation column rectification, methanol distillation column tower
The recovery methanol that still flows out mixes with fresh methanol, returns MTBE methyltertiarvbutyl ether reactor and continues reaction；Water scrubber overhead enters
Entering essence isobutene. tower rectification to separate, and obtain high-purity isobutylene product at tower top, tower reactor obtains MTBE, tert-butyl alcohol product.
Isobutene. production method the most according to claim 1, it is characterised in that the operating condition on absorption tower is: operation gauge pressure
0.88～1.22MPa, operation temperature 50～70 DEG C.
Isobutene. production method the most according to claim 1, it is characterised in that the operating condition of solvent recovery tower is: operation table
Pressure 0.72～1.14MPa, operation temperature 70～140 DEG C.
Isobutene. production method the most according to claim 1, it is characterised in that the operating condition of lightness-removing column is: operation gauge pressure
1.86～2.34MPa, operation temperature 65～145 DEG C.
Isobutene. production method the most according to claim 1, it is characterised in that the operating condition of MTBE methyltertiarvbutyl ether reactor is: adopt
Using fixed bed reactors structural shape, catalyst uses macropore strong acid cation exchanger resin, operation gauge pressure 0.68～
0.72MPa, operation temperature 45～65 DEG C, material molar ratio is, mixes carbon four: methanol=1:0.42～0.58, and liquid charging stock is empty
Speed is 1.1～1.4 hours-1。
Isobutene. production method the most according to claim 1, it is characterised in that the operating condition of reactive distillation column reaction bed
For: catalyst employing macropore strong acid cation exchanger resin, operation gauge pressure 0.58～0.66MPa, operation temperature 55～95 DEG C,
Reflux ratio 0.8～1.0.
Isobutene. production method the most according to claim 1, it is characterised in that the operating condition of deisobutanizer is: operation table
Pressure 0.54～0.78MPa, operation temperature 44～86 DEG C.
Isobutene. production method the most according to claim 1, it is characterised in that the operating condition of MTBE cracking reactor is: adopt
Using fixed bed reactors structural shape, catalyst uses RKS02 solid acid, operates gauge pressure 0.52～0.68MPa, operates temperature
185～205 DEG C, MTBE feed space velocity is 2.5～3.5 hours-1。
Isobutene. production method the most according to claim 1, it is characterised in that the operating condition of water scrubber is: operation gauge pressure
0.52～0.64MPa, operation temperature 46～82 DEG C.
Isobutene. production method the most according to claim 1, it is characterised in that the operating condition of methanol distillation column is: operation
Gauge pressure 0.02～0.06MPa, operation temperature 64～88 DEG C；Essence isobutene. tower operating condition be: operation gauge pressure 0.46～
0.66MPa, operation temperature 45～75 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110526796A (en) * | 2019-08-30 | 2019-12-03 | 凯瑞环保科技股份有限公司 | It is a kind of to provide the device and method of four raw material of carbon for MTBE downstream unit |
| CN112441866A (en) * | 2019-09-04 | 2021-03-05 | 中国石油化工股份有限公司 | Method for producing n-butene from isobutene |
| CN112441865A (en) * | 2019-09-04 | 2021-03-05 | 中国石油化工股份有限公司 | Method for preparing butene-2 from isobutene |
| CN115073254A (en) * | 2022-06-15 | 2022-09-20 | 宁波昊德化学工业股份有限公司 | Production method and production equipment of isobutene |
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