CN108410502A - The processing method of by-product after the desulfurization of methyl tertiary butyl ether(MTBE) and the production of methyl tertiary butyl ether(MTBE) and after-treatment device - Google Patents
The processing method of by-product after the desulfurization of methyl tertiary butyl ether(MTBE) and the production of methyl tertiary butyl ether(MTBE) and after-treatment device Download PDFInfo
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- CN108410502A CN108410502A CN201710071562.9A CN201710071562A CN108410502A CN 108410502 A CN108410502 A CN 108410502A CN 201710071562 A CN201710071562 A CN 201710071562A CN 108410502 A CN108410502 A CN 108410502A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The present invention relates to the production field of methyl tertiary butyl ether(MTBE), production and the after-treatment device of the processing method and a kind of methyl tertiary butyl ether(MTBE) of the by-product after a kind of desulfurization of methyl tertiary butyl ether(MTBE) are disclosed.It the treating method comprises：By the by-product after the desulfurization with coker gasoline according to no more than 0.1：1 ratio mixing carries out hydrogenation reaction as hydrogenating materials；Wherein, the by-product after the desulfurization contain the sulfur-containing compound of the 2 20 weight % in terms of element sulphur, 8 20 weight % aromatic hydrocarbons and 0 60 weight % isobutene dimer.It using method and apparatus provided by the invention, had not only solved the problems, such as that the easy coking intractability of isobutene dimer was big, but also has solved the problems, such as that aromatic component and sulfur component influence follow up device long period even running, high-efficiency environment friendly.
Description
Technical field
The present invention relates to the production fields of methyl tertiary butyl ether(MTBE), and in particular, to after a kind of desulfurization of methyl tertiary butyl ether(MTBE)
By-product processing method and a kind of methyl tertiary butyl ether(MTBE) production and after-treatment device.
Background technology
Methyl tertiary butyl ether(MTBE), english abbreviation are MTBE (methyl tert-butyl ether), are usually used in unleaded gas
As anti-knock agent, also there is extensive use in chemical industry and biological field.
In the 1970s, MTBE starts to be paid attention to by people as the gasoline blend component for improving octane number.MTBE
Basic octane number RON：118, research octane number (RON) 115, motor octane number MON：100, it is excellent gasoline high-octane rating
Additive and anti-knock agent.Chemical oxygen content is much lower compared with methanol, is conducive to warming up and saves fuel, evaporation latent heat is low, to cold start-up
Favorably, it is usually used in the blending of unleaded gas and low lead oil.MTBE can be dissolved each other without lamination with gasoline with arbitrary proportion,
When being reconciled with gasoline component, there is good reconciliation effect, the octane number that reconciles is higher than its clear octane number.MTBE chemical property is stablized,
Oxygen content is relatively high, can significantly improve motor vehicle exhaust emission, reduces the content of carbon monoxide in tail gas.And efficiency of combustion
Height can inhibit the generation of ozone.It can substitute lead tetraethide as anti-knock agent, produce unleaded gas.There are about 95% now
MTBE be used as oxygenate in octane enhancer and gasoline.
The important source material of catalytic liquefaction gas and methanol as MTBE devices, in the significant process of etherification reaction, catalytic liquid
The mercaptan sulfur changed in gas produces methyl tertbutyl thioether grade high sulphur component with isobutene etherification reaction.It is de- in MTBE products simultaneously
The high sulphur component produced in extraction antigum inhibitor, with reaction process is added during sulphur collectively as desulfurizing byproduct.This part
Product all has toxicity to the mankind and mammality, is handled.
After MTBE product desulfurizing tower extraction and separation, the desulfuration byproduct of MTBE products contains 10% or so aromatic hydrocarbons
And 50~60% isobutene dimer, go conventional hydro refining plant to handle, reactor temperature rises relatively low, while isobutene dimerization
After polymerization reaction easily occurs for object, generates the situation of coking, is unfavorable for the smooth long term running of hydrogenation plant, while hydrogenated products
Usually as ethylene raw, higher arene content has larger impact to the operation of ethylene unit.
There are four classes in the country to MTBE desulfurizing byproduct main processing ways at present：
1, the vulcanizing agent for reforming hydrogenation catalyst is made.The vulcanizing agent dosage for reforming hydrogenation catalyst is less, only in the rank that goes into operation
Section can vulcanize raw catelyst, can not consume the quantum of output of MTBE product desulfurization equipment byproducts.Desulfurizing byproduct simultaneously
In component it is complex, composition fluctuation is larger, and the toluene containing higher proportion easily influences the sulphur of catalyst as vulcanizing agent
Change effect.
2, it is fed as disulphide comprehensive utilization device.Isolate pure dimethyl disulfide, Methylethyl disulphide into
Row utilizes.But this method needs special corollary apparatus, cost to increase, while because desulfurizing byproduct amount is less, and wherein
Disulphide content is relatively low, and by-product is more, does not have the condition of unified recycling.
3, environmental protection company is transferred to be uniformly processed.By-product can not continuously go out device after desulfurization, need to be at desulfurizing tower bottom accumulative one
After quantitative, environmental protection company is sent to by tank car, technological parameter fluctuation is big, unstable product quality；Transfer to environmental protection company handling
With higher, operational risk is big, while the aromatic hydrocarbons containing higher proportion in desulfurizing byproduct, causes the waste of resource, economy effect
Benefit is poor.By-product mostly uses greatly the processing of this thinking after desulfurization at present.
4, direct hydrogenation is handled.In direct hydrogenation treatment process, it is still necessary to be wanted to hydrogen purity, sulfur content, water content etc.
Seek extremely harsh as-reduced metal catalyst.By-product after a large amount of desulfurization is directly mixed in common hydro-refining unit charging
Reason, but because reactor pressure decrease rise it is too fast due to must not be without shutdown process.Therefore the direct conventional hydro of light dydrocarbon material is handled,
In actual mechanical process, there is larger difficulty.
Therefore, the processing method and phase of the by-product after the desulfurization of a kind of efficient and environmentally friendly methyl tertiary butyl ether(MTBE) are developed
The device answered is very necessary.
Invention content
In order to overcome the processing method efficiency of the by-product after methyl tertiary butyl ether(MTBE) desulfurization in the prior art it is low, by by-product
The defects of influence of fluctuations is big is formed, a kind of processing method of the by-product after the desulfurization of methyl tertiary butyl ether(MTBE) is provided, using this
Method had not only solved the problems, such as that the easy coking intractability of isobutene dimer was big, but also has solved aromatic component and sulfur component shadow
The problem of ringing follow up device long period even running, high-efficiency environment friendly.
Specifically, in a first aspect, the present invention provides a kind of processing sides of the by-product after desulfurization of methyl tertiary butyl ether(MTBE)
Method, this method include：By the by-product after the desulfurization with coker gasoline according to no more than 0.1：1 ratio mixing is used as plus hydrogen
Raw material carries out hydrogenation reaction；Wherein, the by-product after the desulfurization contains the sulfur-bearing chemical combination of the 2-20 weight % in terms of element sulphur
The isobutene dimer of object, the aromatic hydrocarbons of 8-20 weight % and 0-60 weight %.
Second aspect, the present invention provides a kind of production of methyl tertiary butyl ether(MTBE) and after-treatment devices, wherein the device packet
It includes four head tank of carbon, methanol feedstock tank, methyltertiarvbutyl ether reactor, catalytic distillation tower, extraction antigum inhibitor head tank, desulfurizing tower and adds hydrogen list
Member, wherein the side line of the outlet of four head tank of the carbon and the outlet of the methanol feedstock tank with the methyltertiarvbutyl ether reactor enters
Mouth connection, the tower top outlet of the methyltertiarvbutyl ether reactor are connect with the side line entrance of the catalytic distillation tower, the catalytic distillation tower
Bottom of tower outlet and it is described extract antigum inhibitor head tank outlet connect with the side line entrance of the desulfurizing tower, the desulfurizing tower
Bottom of tower outlet connect with the entrance of the hydrogenation unit.
Using method and apparatus provided by the invention, have the advantage that：
1, it is used as coker gasoline mixed hydrogenation raw material after mixing refining, is carried out after the by-product after desulfurization is mixed with coker gasoline
The production of the means such as hydrogen, cooling, separation, stripping is added to refine naphtha as ethylene cracking material.It is secondary after desulfurization by effectively controlling
Aromatic hydrocarbons in product and dimer content, control coker gasoline mix refining ratio, effectively prevent reactor and high pressure heat exchanger coking,
Situations such as pressure difference rises.Simultaneously because coker gasoline and by-product after desulfurization mix refining, Hydrogenation of Coker Gasoline fever according to a certain percentage
Amount, which meets, exchanges heat raw material to reacting initial temperature condition, avoids arene content is higher from cannot be satisfied Wen Sheng, has saved plus hydrogen fills
Reaction heating furnace operating cost is set, plant energy consumption is reduced.
2, processing method of the invention so that the by-product after MTBE desulfurization is dealt carefully with, and turns waste into wealth, it is therefore prevented that
Pollution of the desulfurizing agent industrial wastes to environment, but so that toluene, isobutene dimer, methyl tertbutyl thioether etc. are used as coking vapour
The raw material of oil plus hydrogen is recycled so that recovery and treatment method of the invention forms coherent production line.At recycling
Reason can improve comprehensive yield, reduce cost, obtain prodigious economic benefit.
3, processing method technological process of the invention is simple, stablizes, and creative is required using coker gasoline mixed hydrogenation,
Using coker gasoline as diluent, the stable operation of downstream unit is ensured.
4, present invention ensure that by-product long period stable delivery, each process chart index are flat after the desulfurization of desulfurizing tower bottom of tower
Surely, MTBE products desulfurization effect is obviously improved.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the production of methyl tertiary butyl ether(MTBE) provided by the invention and a kind of preferred embodiment of after-treatment device.
Reference sign
1 carbon, four head tank, 2 methanol feedstock tank
3 methyltertiarvbutyl ether reactor, 4 catalytic distillation tower
5 extraction antigum inhibitor head tank, 6 desulfurizing tower
7 hydrogenation units
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of processing method of the by-product after desulfurization of methyl tertiary butyl ether(MTBE), this method includes：It will
By-product after the desulfurization is with coker gasoline according to no more than 0.1：1 ratio mixing is carried out as hydrogenating materials plus hydrogen is anti-
It answers；Wherein, the by-product after the desulfurization contains the sulfur-containing compound of the 2-20 weight % in terms of element sulphur, 8-20 weight %
The isobutene dimer of aromatic hydrocarbons and 0-60 weight %.
Preferably, the by-product after the desulfurization and coker gasoline are according to 0.01-0.09：1 ratio mixing is used as plus hydrogen
Raw material, more preferably 0.02-0.08：1.
Preferably, the by-product after the desulfurization contains sulfur-containing compound, the 9-19 of the 3-18 weight % in terms of element sulphur
The isobutene dimer of the aromatic hydrocarbons and 1-60 weight % of weight %.It is highly preferred that the by-product after the desulfurization contains with sulphur member
The isobutene dimer of the sulfur-containing compound of the 4-15 weight % of element meter, the aromatic hydrocarbons and 1-50 weight % of 10-18 weight %.
According to the present invention, due to the by-product after the desulfurization preparation process the step of (3) in used the anti-glue of extraction
Agent (such as can be Hebei exquisiteness Science and Technology Ltd. the trade mark be GL extraction antigum inhibitor product), extract the ingredient of antigum inhibitor
Not entire disclosure, thus also contain in by-product after desulfurization in the present invention come from it is unknown in the extraction antigum inhibitor
Ingredient.In addition, a small amount of methyl tertiary butyl ether(MTBE) (MTBE) and the tert-butyl alcohol can also be contained in by-product after the desulfurization.It is preferred that
, in the present invention in the by-product after desulfurization, on the basis of the total weight of the by-product after the desulfurization, the MTBE's contains
Amount is 0.1-5 weight %, and the content of the tert-butyl alcohol is 1 weight % or less.
In the present invention, the type of the sulfur-containing compound in methyl tert-butyl ether product can be according to the source of four raw material of carbon
It is predicted.The sulfur-containing compound may include one or more in following sulfur-containing compound：Hydrogen sulfide, carbonyl sulfur, first
Mercaptan, ethyl mercaptan, methyl sulfide, propanethiol, isopropyl mercaptan, tert-butyl mercaptan, n-propyl mercaptan, methyl ethyl sulfide, sec-butyl thioalcohol, first
Base isopropyl thioether, isobutyl mercaptan, diethyl thioether, n-butyl mercaptan, methyl n-propyl thioether, methyl tertbutyl thioether, diformazan
Two sulphur of base, ethylisopropyl base thioether, isoamyl mercaptan, methyl sec-butylsulfide, ethyl n-propyl thioether, methyl n-butyl sulfide,
N-amyl mercaptan, Methylethyl disulfide, propyl iso-propyl thioether, diη-propyl thioether, ethyl-butyl thioether, two sulphur of diethyl
Ether, positive hexanethiol, n-heptanthiol and benzothiophene.
Include sulfur removal technology during synthesizing methyl tertbutyl ether according to the present invention, it is big after the sulfur removal technology
Partial sulfide is all transformed to thioether, it is also possible to remain the mercaptan that minute quantity does not remove.Using the hand of acid-base neutralization reaction
Section can distinguish thioether or mercaptan.For example, alkali (such as a small amount of sodium hydroxide solution is added) can be added into MTBE products
The chromatogram of the MTBE products after gas-chromatography-sulfur chemiluminescence detection method measurement plus alkali is used again, if relative to not adding
Peak for the chromatogram of alkali under some retention time disappears, on the contrary then be then under retention time be then mercaptan at this
Thioether.According to a kind of preferred embodiment, in the by-product after the desulfurization, the total weight with the sulfur-containing compound is
The content of benchmark, thioether is 80-90 weight %, and the content of mercaptan is 10-20 weight %.
In the present invention, due to the composition of the by-product after desulfurization complexity, so can also be defined with boiling range.Example
Such as, the initial boiling point of the by-product after the desulfurization can be 58-68 DEG C, and the end point of distillation can be 120-200 DEG C.
In the present invention, the aromatic hydrocarbons refers to the hydrocarbon containing phenyl ring.
In the present invention, the type of the isobutene dimer can be the conventional selection of this field.Isobutene dimer
Type generally include 2,4,4- trimethyl -1- amylenes (2,4,4-trimethyl-1-pentene, α-DIB) and/or 2,4,4-
Trimethyl -2- amylenes (2,4,4-trimethyl-2-pentene, β-DIB) are in addition also possible in isobutene dimer containing 2,
3,4- trimethylpentenes.
In the present invention, the method can also include that the by-product after desulfurization is prepared according to following procedure：
(1) under the conditions of etherification reaction, four raw material of carbon is contacted with methanol；
(2) product that step (1) obtains is passed through into catalytic distillation tower；
(3) enter desulfurizing tower after mixing the catalytic distillation tower tower bottom product that step (2) obtains with extraction antigum inhibitor to carry out
Desulfurization process obtains the by-product after desulfurization from desulfurizing tower bottom of tower.
According to the present invention, four raw material of the carbon can be the conventional selection of this field, such as can be gas fractionation unit
The mixing C-4-fraction of production, the content of isobutene can be 15-20 weight % in four raw material of carbon.
In the present invention, the condition of the etherification reaction can change in wide range.For example, the etherification reaction item
Part includes：Temperature can be 55-80 DEG C, preferably 60-73 DEG C.Within the above range by the condition control of etherification reaction, it both carried
High light component mercaptan sulfur is converted into thioether sulphur, and then improves the desulfurization effect of MTBE products, can also reduce as possible different
The generation of butene dimer.In addition, for the other conditions of etherification reaction include catalyst type and dosage, reaction pressure and
Raw material than etc. all can be this field conventional selection.For example, the catalyst of the etherification reaction can be large aperture highly acid
Cation exchange resin, such as can be the product that the trade mark purchased from Dandong jewel company is D005-II；Pressure can be 0.7-
The molar ratio of 0.9MPa, methanol and isobutene can be 0.8-1:1, preferably 0.85-0.95:1.Unless stated otherwise, this hair
Pressure in bright is gauge pressure.
It should be noted that the temperature raising of etherification reaction, which is conducive to raising light component mercaptan sulfur, is converted into thioether
Sulphur, but higher temperature can also be conducive to the generation of isobutene dimer.On the contrary, lower etherification reaction temperature is conducive to
It reduces the generation of isobutene dimer but is detrimental to the conversion of sulphur.Sulfur-containing compound and isobutene two in by-product after desulfurization
The too high levels of polymers are unfavorable for hydrogenation reaction.After etherification reaction temperature in the present invention can ensure the desulfurization subsequently obtained
By-product in sulfur-containing compound and isobutene dimer content and coordinate ratio appropriate (be no more than 0.1:1) after meeting
The requirement of continuous hydrogenation reaction.
According to the present invention, methyl tertiary butyl ether(MTBE), side reaction product, not anti-is usually contained in the obtained product of step (1)
Carbon four, residual methanol and the unconverted isobutene answered.Methanol and carbon four can form azeotropic mixture under a certain pressure, so can
To use catalytic distillation technology, realize that the most of of remaining isobutene converts and be substantially free of methanol in MTBE products.According to
A kind of specific embodiment, the product that step (1) obtains pass through catalytic distillation tower.The MTBE generated is reacted by bottom of tower azeotropic device
Heating, can form low-boiling azeotropic mixture with unreacted methanol and remaining carbon four and be detached in catalytic distillation tower, not instead
The methanol and remaining carbon four answered form low-boiling copolymer and can be distillated from catalytic distillation column overhead.
According to the present invention, the type and structure of the catalytic distillation tower can be the conventional selection of this field.For example, described
Catalytic distillation tower can be divided into three parts.Tower lower part is stripping section, using structured packing；It is conversion zone, conversion zone in the middle part of tower
Equipped with stem-based catalyst, point ten sections of beds；Tower top is rectifying section, using structured packing.Tower top is configured with return tank to control
The pressure of tower.
According to the present invention, the service condition of the catalytic distillation tower includes：Feeding temperature can be 65-75 DEG C；Tower top temperature
Degree can be 50-70 DEG C；Tower pressure (including tower top pressure and tower bottom pressure) can be 0.3-0.75MPa, preferably 0.6-
0.65MPa；Column bottom temperature can be 120-140 DEG C, preferably 125-130 DEG C；Return tank temperature can be 30-60 DEG C, reflux
Pressure tank can be 0.3-0.75MPa；Reflux ratio (weight) can be 0.7-1.By the column bottom temperature for improving catalytic distillation tower
To the scope of the present invention, the olefin(e) centent in MTBE products can be controlled within 5 weight %.
According to the present invention, the product that step (1) obtains is passed through into catalytic distillation tower；It is obtained from the tower top of the catalytic distillation tower
Four component of carbon after to ether, the tower bottom product obtained from catalytic distillation tower bottom of tower, i.e. MTBE products.In the present invention, the MTBE
Product each means the methyl tertiary butyl ether(MTBE) containing impurity.
Other than aforementioned present invention disclosure, the production of remaining MTBE and operating method and condition all can be this
The conventional selection in field.For example, " PetroChina Company Ltd. company standard Q/SY HS 1008- can be referred to
2004, MTBE device operating instructions ", the method in order to which the present invention is described more fully with, this hair is introduced by the full text of above-mentioned standard
It is bright.Other than present disclosure, remaining can be obtained from above-mentioned standard.
According to the present invention, enter after the catalytic distillation tower tower bottom product that step (2) obtains is mixed with extraction antigum inhibitor de-
Sulphur tower carries out desulfurization process.
In the present invention, the technology of the desulfurization process of MTBE products can be that MTBE extracts redistillation technology, or
MTBE complexometry deep desulfuration technologies, preferably MTBE extract redistillation technology.The MTBE extractions redistillation technology is to utilize
Desulfurizing tower (extraction distillation column) implements extraction redistillation to MTBE, and the MTBE of low-sulfur is steamed from tower top, and high-sulfur fraction is followed in bottom of tower
The byproduct fraction of ring, highly enriched sulfur-containing compound is extracted out from bottom of tower, can be used for subsequent hydrogenation reaction.According to one kind
Preferred embodiment reduces the loss of MTBE in order to improve desulfurization effect, prevents bottom of tower generation polycondensation and coking anti-
It answers, is preferably added to extraction antigum inhibitor and carries out redistillation.The extraction antigum inhibitor can be commercially available, for example, can be purchased from
The trade mark of Hebei exquisiteness Science and Technology Ltd. is the product that GL extracts antigum inhibitor.The dosage of the extraction antigum inhibitor can be larger
It is changed in range, for example, the catalytic distillation tower tower bottom product (i.e. MTBE products) relative to 1kg, the extraction antigum inhibitor
Dosage be 500-900mg, preferably 600-800mg.Dosage by that will extract antigum inhibitor controls within the above range, can be with
Make the arene content in the by-product after desulfurization within 20 weight %.
In the present invention, the condition of the desulfurization process includes：Feeding temperature can be 55-65 DEG C, and tower top temperature can be with
It it is 55-75 DEG C, column bottom temperature can be 80-120 DEG C, preferably 85-100 DEG C；Tower pressure (including tower top pressure and tower bottom pressure)
Can be 0.03-0.05MPa, preferably 0.035-0.045MPa.The column bottom temperature of desulfurization process using the present invention and extraction
The arene content of by-product after desulfurization can be controlled within 20 weight %, and can produce sulphur by the dosage of antigum inhibitor
Content is less than the methyl tertiary butyl ether(MTBE) of 15mg/kg.
In the present invention, the hydrogenation reaction can carry out in hydrogenation reactor, and what the hydrogenation reaction used urges
Agent can be the conventional selection of this field, such as can be that the trade mark that Sinopec Fushun Petrochemical Research Institute produces is
The product of FH-40C.The condition of the hydrogenation reaction includes：Hydrogen to oil volume ratio can be 250-600, preferably 300-500；Temperature
Degree can be 300-400 DEG C, preferably 300-350 DEG C；Pressure can be 3-3.6MPa, and bed pressure drop is not more than 0.35MPa, former
Expect that air speed can be 1-2h-1。
In the present invention, the composition of the coker gasoline can be the conventional selection of this field.For example, the coker gasoline
Initial boiling point be 30-50 DEG C, the end point of distillation be 200-240 DEG C.Preferably, the initial boiling point of the coker gasoline is 30-40 DEG C, is evaporated eventually
Point is 210-230 DEG C.
The present invention also provides a kind of production of methyl tertiary butyl ether(MTBE) and after-treatment devices, as shown in Figure 1, the device includes
Four head tank 1 of carbon, methyltertiarvbutyl ether reactor 3, catalytic distillation tower 4, extracts antigum inhibitor head tank 5, desulfurizing tower 6 and adds methanol feedstock tank 2
Hydrogen unit 7, wherein four head tank 1 of the carbon outlet and the methanol feedstock tank 2 outlet with the methyltertiarvbutyl ether reactor 3
Side line entrance connection, the tower top outlet of the methyltertiarvbutyl ether reactor 3 is connect with the side line entrance of the catalytic distillation tower 4, described
The bottom of tower of catalytic distillation tower 4 exports and the outlet of the extraction antigum inhibitor head tank 5 connects with the side line entrance of the desulfurizing tower 6
It connects, the bottom of tower outlet of the desulfurizing tower 6 is connect with the entrance of the hydrogenation unit 7.
According to the present invention, four head tank 1 of the carbon is used to provide carbon four raw materials for methyltertiarvbutyl ether reactor 3, and methanol feedstock tank 2 is used
In providing methanol feedstock for methyltertiarvbutyl ether reactor 3, extraction antigum inhibitor head tank 5 for desulfurizing tower 6 for providing extraction antigum inhibitor.It is above-mentioned
There is no particular limitation for the shapes and sizes of tank, can be the conventional selection of this field.
In accordance with the present invention it is preferred that being provided with four raw material of carbon between four head tank 1 of the carbon and the methyltertiarvbutyl ether reactor 3
Pump 8, for four raw material of carbon to be pressurized.There is no particular limitation for the type of four raw material of carbon pump, can be the routine of this field
Selection.Such as can be the model 150AY that purchase pumps industry production from Shenyang Ge RuideII150 pump.
In accordance with the present invention it is preferred that it is provided with heat exchanger 9 between four raw material of carbon pump 8 and the methyltertiarvbutyl ether reactor 3,
For the mixture of four raw material of carbon and methanol and the MTBE products of 3 bottom of tower of methyltertiarvbutyl ether reactor to be exchanged heat.Heat exchanger 9 it is specific
Type is known to those skilled in the art.
According to a kind of preferred embodiment of the present invention, methanol feedstock tank 2 is located at the upstream of reacting replacing heat device 9.
According to the present invention, the methyltertiarvbutyl ether reactor 3 carries out etherification reaction for four raw material of carbon and methanol and prepares MTBE.It is described
The type of methyltertiarvbutyl ether reactor 3 can be the conventional selection of this field, dawn known to those skilled in the art.The etherification reaction
Condition has been described above, and details are not described herein.
According to the present invention, the catalytic distillation tower 4 is for detaching MTBE and four raw material of unreacted methanol and carbon.Reaction life
At MTBE by bottom of tower azeotropic device heat, can form low-boiling azeotropic mixture with unreacted methanol and remaining carbon four and urge
Change separation in destilling tower, unreacted methanol and remaining carbon four form low-boiling copolymer can be from catalytic distillation column overhead
It distillates.The type and structure of the catalytic distillation tower 4 can be the conventional selection of this field.For example, the catalytic distillation tower can
To be divided into three parts.Tower lower part is stripping section, using structured packing；It is conversion zone in the middle part of tower, conversion zone is catalyzed equipped with butt
Agent, point ten sections of beds；Tower top is rectifying section, and using structured packing, tower top is configured with return tank with the pressure of control tower.
According to the present invention, the MTBE products that the desulfurizing tower 6 is used to obtain the bottom of tower of catalytic distillation tower 4 carry out at desulfurization
Reason.The specific type and structure of the desulfurizing tower 6 are the conventional selection of this field.The condition of the desulfurization process is above
It is described, details are not described herein.
In the present invention, hydrogenation reaction of the hydrogenation unit 7 for the by-product after the desulfurization.The hydrogenation unit
7 can be Hydrogenation of Coker Gasoline equipment.The Hydrogenation of Coker Gasoline equipment can be the conventional selection of this field, for example, institute
It may include weighted BMO spaces reactor, hydrogenation reactor, fractionating system and desulphurization system to state Hydrogenation of Coker Gasoline equipment.It is described
The condition of hydrogenation reaction has been described above, and details are not described herein.
According to the present invention, the tower top of the desulfurizing tower 6 obtains the MTBE after desulfurization, preferably belonging to the tower top of desulfurizing tower 6 go out
Mouth is connect with the MTBE collection devices after desulfurization.
The present invention will be described in detail by way of examples below.In following embodiment,
Extraction antigum inhibitor is that the trade mark purchased from Hebei exquisiteness Science and Technology Ltd. is the product that GL extracts antigum inhibitor.Add hydrogen anti-
The catalyst answered is the product that the trade mark of Sinopec Fushun Petrochemical Research Institute production is FH-40C.The coker gasoline used
Initial boiling point be 40 DEG C, the end point of distillation be 220 DEG C.
The test of the sulfur-containing compound in by-product, aromatic hydrocarbons and isobutene dimer after desulfurization is according to GB/T10410-
2008 and GB/T17040-2008 is carried out.
Embodiment 1
The present embodiment be used to illustrate the by-product after the desulfurization of methyl tertiary butyl ether(MTBE) provided by the invention processing method and
The production of methyl tertiary butyl ether(MTBE) and after-treatment device
As shown in Figure 1, the side of the outlet of four head tank 1 of carbon and the outlet of methanol feedstock tank 2 with the methyltertiarvbutyl ether reactor 3
Line entrance connects, and four raw material of carbon pump 8 and reacting replacing heat device 9 are disposed between four head tank 1 of carbon and methyltertiarvbutyl ether reactor 3.First
Raw polyol tank 2 is located at the upstream of methyltertiarvbutyl ether reactor 3.The side of the tower top outlet of the methyltertiarvbutyl ether reactor 3 and the catalytic distillation tower 4
Line entrance connects, the outlet of the bottom of tower of the catalytic distillation tower 4 and the outlet for extracting antigum inhibitor head tank 5 with the desulfurization
The side line entrance of tower 6 connects, and the bottom of tower outlet of the desulfurizing tower 6 is connect with the entrance of the hydrogenation unit 7.
Four raw material of carbon come from gas fractionation unit enters four head tank 1 of carbon, and four raw material of carbon in head tank is former through carbon four
It is mixed to form mixed material with the methanol from methanol feedstock tank 2 after 8 supercharging of material pump, subsequently enters reacting replacing heat device 9, mixture
Material enters methyltertiarvbutyl ether reactor 3 after heat exchange, carries out etherification reaction under the action of catalyst.Then by etherification reaction product by urging
Change destilling tower 4.MTBE is constantly detached in catalytic distillation tower 4, so that etherification reaction is carried out to depth, isobutene is made to reach more
High conversion ratio.It in catalytic distillation tower 4, reacts the MTBE of generation and is heated by bottom of tower azeotropic device, and unreacted methanol and remain
The low-boiling azeotropic mixture that remaining carbon four is formed detaches in catalytic distillation tower, and unreacted methanol and remaining carbon four form low
The copolymer of boiling point is distillated from catalytic distillation column overhead, and MTBE products are flowed out from catalytic distillation tower bottom.Subsequent MTBE products with
Extraction antigum inhibitor from extraction antigum inhibitor head tank 5 is mixed into desulfurizing tower 5 and carries out desulfurization process.It is obtained from desulfurization column overhead
MTBE after desulfurization obtains the by-product after desulfurization from desulfurizing tower bottom of tower, and the by-product after desulfurization enters hydrogenation unit 7 and coking
Gasoline mixing carries out hydrogenation reaction.
Wherein, the content of isobutene is 15 weight % in four raw material of carbon.
Etherification reaction is using large aperture storng-acid cation exchange resin (Dandong jewel company, D005-II) as catalysis
Agent, etherification reaction condition include：The molar ratio of methanol and isobutene is 0.9：1, temperature is 60 DEG C.
The service condition of catalytic distillation tower is：Feeding temperature is 65 DEG C, and tower top temperature is 50 DEG C, and tower top pressure is
0.55MPa, 120 DEG C of column bottom temperature, tower bottom pressure 0.61MPa；Return tank temperature is 50 DEG C, and reflux pressure tank is 0.55MPa；
Reflux ratio (weight) is 0.7.
The service condition of desulfurizing tower is：Feeding temperature is 60 DEG C, and tower top temperature is 60 DEG C, tower top pressure 0.03MPa, tower
80 DEG C of bottom temperature, tower bottom pressure 0.04MPa.Relative to the MTBE products of 1kg, the dosage for extracting antigum inhibitor is 700mg.
By-product after desulfurization contains the sulfur-containing compound of 9 weight %, the aromatic hydrocarbons of 18 weight %, 40 weights in terms of element sulphur
Measure the MTBE of the isobutene dimer and 1 weight % of %.
By-product after above-mentioned desulfurization is with coker gasoline according to 0.03：1 ratio mixing is used as hydrogenating materials.
The condition of hydrogenation reaction includes：Catalyst is that the trade mark of Sinopec Fushun Petrochemical Research Institute production is FH-
The catalyst of 40C, hydrogen to oil volume ratio 400, temperature are 300 DEG C, pressure 3.4MPa, feed space velocity 1.7h-1。
Whole device entirety even running, the by-product after MTBE desulfurization are effectively addressed.
Embodiment 2
The present embodiment be used to illustrate the by-product after the desulfurization of methyl tertiary butyl ether(MTBE) provided by the invention processing method and
The production of methyl tertiary butyl ether(MTBE) and after-treatment device
It is carried out according to the device and method of embodiment 1, unlike：
The content of isobutene is 17 weight % in four raw material of carbon.
Etherification reaction condition includes：The molar ratio of methanol and isobutene is 0.85：1, temperature is 67 DEG C.
The service condition of catalytic distillation tower is：Feeding temperature is 70 DEG C, and tower top temperature is 55 DEG C, and tower top pressure is
0.6MPa, 130 DEG C of column bottom temperature, tower bottom pressure 0.63MPa；Return tank temperature is 55 DEG C, and reflux pressure tank is 0.63MPa；
Reflux ratio (weight) is 0.7.
The service condition of desulfurizing tower is：Feeding temperature is 65 DEG C, and tower top temperature is 70 DEG C, tower top pressure 0.04MPa, tower
100 DEG C of bottom temperature, tower bottom pressure 0.05MPa.Relative to the MTBE products of 1kg, the dosage for extracting antigum inhibitor is 600mg.
By-product after desulfurization contains the sulfur-containing compound of 6 weight %, the aromatic hydrocarbons of 15 weight %, 55 weights in terms of element sulphur
Measure the MTBE of the isobutene dimer and 2 weight % of %.
By-product after above-mentioned desulfurization is with coker gasoline according to 0.05：1 ratio mixing is used as hydrogenating materials.
The condition of hydrogenation reaction includes：Catalyst is that the trade mark of Sinopec Fushun Petrochemical Research Institute production is FH-
The catalyst of 40C, hydrogen to oil volume ratio 450, temperature are 310 DEG C, pressure 3.4MPa, feed space velocity 1.7h-1。
Whole device entirety even running, the by-product after MTBE desulfurization are effectively addressed.
Embodiment 3
The present embodiment be used to illustrate the by-product after the desulfurization of methyl tertiary butyl ether(MTBE) provided by the invention processing method and
The production of methyl tertiary butyl ether(MTBE) and after-treatment device
It is carried out according to the device and method of embodiment 1, unlike：
The content of isobutene is 20 weight % in four raw material of carbon.
Etherification reaction condition includes：The molar ratio of methanol and isobutene is 0.95：1, temperature is 73 DEG C.
The service condition of catalytic distillation tower is：Feeding temperature is 75 DEG C, and tower top temperature is 60 DEG C, and tower top pressure is
0.65MPa, 135 DEG C of column bottom temperature, tower bottom pressure 0.7MPa；Return tank temperature is 60 DEG C, and reflux pressure tank is 0.65MPa；
Reflux ratio (weight) is 0.7.
The service condition of desulfurizing tower is：Feeding temperature is 55 DEG C, and tower top temperature is 67 DEG C, tower top pressure 0.05MPa, tower
85 DEG C of bottom temperature, tower bottom pressure 0.03MPa.Relative to the MTBE products of 1kg, the dosage for extracting antigum inhibitor is 800mg.
By-product after desulfurization contains the sulfur-containing compound of 4 weight %, the aromatic hydrocarbons of 10 weight %, 60 weights in terms of element sulphur
Measure the MTBE of the isobutene dimer and 1 weight % of %.
By-product after above-mentioned desulfurization is with coker gasoline according to 0.08：1 ratio mixing is used as hydrogenating materials.
The condition of hydrogenation reaction includes：Catalyst is that the trade mark of Sinopec Fushun Petrochemical Research Institute production is FH-
The catalyst of 40C, hydrogen to oil volume ratio 470, temperature are 320 DEG C, pressure 3.3MPa, feed space velocity 1.7h-1。
Whole device entirety even running, the by-product after MTBE desulfurization are effectively addressed.
Embodiment 4
The present embodiment be used to illustrate the by-product after the desulfurization of methyl tertiary butyl ether(MTBE) provided by the invention processing method and
The production of methyl tertiary butyl ether(MTBE) and after-treatment device
It is carried out according to the device and method of embodiment 1, unlike：The temperature of etherification reaction is 55 DEG C.
By-product after desulfurization contains the sulfur-containing compound of 20 weight %, the aromatic hydrocarbons of 20 weight %, 5 weights in terms of element sulphur
Measure the MTBE of the isobutene dimer and 3 weight % of %.
By-product after above-mentioned desulfurization is with coker gasoline according to 0.03：1 ratio mixing is used as hydrogenating materials.Hydrogenation reaction
Condition according to embodiment 1 condition carry out.
Whole device entirety even running, the by-product after MTBE desulfurization are effectively addressed.
Comparative example 1
The comparative example is used to illustrate the processing method of the by-product after the desulfurization of the methyl tertiary butyl ether(MTBE) of reference
It is carried out according to the device and method of embodiment 1, unlike, the by-product after the desulfurization is pressed with coker gasoline
According to 0.5：1 ratio mixing carries out hydrogenation reaction as hydrogenating materials, and as a result hydrogenation reactor temperature lifting is low, under reaction temperature
Drop, the by-product after MTBE desulfurization, which is unable to get, to be effectively treated.
Comparative example 2
The comparative example is used to illustrate the processing method of the by-product after the desulfurization of the methyl tertiary butyl ether(MTBE) of reference
It is carried out according to the device and method of embodiment 1, unlike, etherification reaction temperature is 85 DEG C, after final desulfurization
By-product contain the sulfur-containing compound of the 3 weight % in terms of element sulphur, 19 weight % aromatic hydrocarbons and 70 weight % isobutene two
Polymers.By-product after above-mentioned desulfurization is subjected to hydrogenation reaction according to the method for embodiment 1, as a result hydrogenation reactor Wen Shengsheng
Height, reaction temperature is higher, and the by-product after MTBE desulfurization, which is unable to get, to be effectively treated.
Comparative example 3
The comparative example is used to illustrate the processing method of the by-product after the desulfurization of the methyl tertiary butyl ether(MTBE) of reference
It is carried out according to the device and method of embodiment 1, unlike, the dosage for extracting antigum inhibitor is 100mg, final desulfurization
By-product afterwards contain the sulfur-containing compound of the 30 weight % in terms of element sulphur, 5 weight % aromatic hydrocarbons and 55 weight % isobutyl
Alkene dimer.By-product after above-mentioned desulfurization is subjected to hydrogenation reaction according to the method for embodiment 1, as a result hydrogenation reactor Wen Sheng
It reduces, reaction temperature declines, and the by-product after MTBE desulfurization, which is unable to get, to be effectively treated, while sulfur content in the MTBE after desulfurization
Exceeded, MTBE's is off quality.
Device and method using the present invention are can be seen that from the result of embodiment and comparative example, can be effectively treated
By-product after the desulfurization of MTBE, and method not using the present invention, increase after MTBE desulfurization the processing cost of by-product and
Environmentally friendly risk, including by-product after desulfurization are unable to get and are effectively treated and/or the sulfur content of MTBE is exceeded off quality.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (13)
1. a kind of processing method of the by-product after desulfurization of methyl tertiary butyl ether(MTBE), which is characterized in that this method includes：It will be described
By-product after desulfurization is with coker gasoline according to no more than 0.1：1 ratio mixing carries out hydrogenation reaction as hydrogenating materials；Its
In, the by-product after the desulfurization contains the aromatic hydrocarbons of the sulfur-containing compound of the 2-20 weight % in terms of element sulphur, 8-20 weight %
With the isobutene dimer of 0-60 weight %.
2. according to the method described in claim 1, wherein, the by-product after the desulfurization is with coker gasoline according to 0.01-0.09：
1 ratio mixing is used as hydrogenating materials.
3. according to the method described in claim 1, wherein, the by-product after the desulfurization contains the weights of the 3-18 in terms of element sulphur
Measure the isobutene dimer of the sulfur-containing compound of %, the aromatic hydrocarbons and 1-60 weight % of 9-19 weight %.
4. method according to claim 1 or 3, wherein the initial boiling point of the by-product after the desulfurization is 58-68 DEG C, eventually
Evaporate is a little 120-200 DEG C.
5. according to the method described in any one of claim 1-4, wherein the method further includes being prepared according to following procedure
By-product after desulfurization：
(1) under the conditions of etherification reaction, four raw material of carbon is contacted with methanol；
(2) product that step (1) obtains is passed through into catalytic distillation tower；
(3) enter desulfurizing tower after mixing the catalytic distillation tower tower bottom product that step (2) obtains with extraction antigum inhibitor and carry out desulfurization
Processing, the by-product after desulfurization is obtained from desulfurizing tower bottom of tower.
6. according to the method described in claim 5, wherein, in step (1), the etherification reaction condition includes：Temperature is 55-
80 DEG C, preferably 60-73 DEG C.
7. according to the method described in claim 5, wherein, the service condition of the catalytic distillation tower includes：Column bottom temperature is
120-140 DEG C, preferably 125-130 DEG C；Tower pressure is 0.3-0.75MPa, preferably 0.6-0.65MPa.
8. according to the method described in claim 5, wherein, relative to the catalytic distillation tower tower bottom product of 1kg, the extraction
The dosage of antigum inhibitor is 500-900mg.
9. according to the method described in claim 5, wherein, the condition of the desulfurization process includes：80-120 DEG C of column bottom temperature, it is excellent
It is selected as 85-100 DEG C；Tower pressure is 0.03-0.05MPa, preferably 0.035-0.045MPa.
10. according to the method described in any one of claim 1-4, wherein the condition of the hydrogenation reaction includes：Hydrogen oil body
Product is than being 250-600, preferably 300-500；Temperature is 300-400 DEG C, preferably 300-350 DEG C；Bed pressure drop is not more than
0.35MPa, feed space velocity 1-2h-1。
11. according to the method described in any one of claim 1-4, wherein the initial boiling point of the coker gasoline is 30-50
DEG C, the end point of distillation is 200-240 DEG C；Preferably, the initial boiling point of the coker gasoline is 30-40 DEG C, and the end point of distillation is 210-230 DEG C.
12. production and the after-treatment device of a kind of methyl tertiary butyl ether(MTBE), which is characterized in that the device include four head tank of carbon (1),
Methanol feedstock tank (2), methyltertiarvbutyl ether reactor (3), catalytic distillation tower (4), extraction antigum inhibitor head tank (5), desulfurizing tower (6) and plus hydrogen
Unit (7), wherein the outlet of four head tank of the carbon (1) and the outlet of the methanol feedstock tank (2) with the etherification reaction
The side line entrance of device (3) connects, the side line entrance of the tower top outlet and the catalytic distillation tower (4) of the methyltertiarvbutyl ether reactor (3)
Connection, the catalytic distillation tower (4) bottom of tower outlet and it is described extract antigum inhibitor head tank (5) outlet with the desulfurizing tower
(6) the bottom of tower outlet of side line entrance connection, the desulfurizing tower (6) is connect with the entrance of the hydrogenation unit (7).
13. device according to claim 12, wherein between four head tank of the carbon (1) and the methyltertiarvbutyl ether reactor (3)
It is provided with four raw material of carbon pump (8)；
Preferably, it is provided with heat exchanger (9) between four raw material of carbon pump (8) and the methyltertiarvbutyl ether reactor (3).
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| CN111521721A (en) * | 2019-02-01 | 2020-08-11 | 株式会社岛津制作所 | Sulfur chemiluminescence detector |
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| CN102827632A (en) * | 2011-06-14 | 2012-12-19 | 中国石油化工股份有限公司 | Method for processing C5 raffinate from ethene cracking |
| CN104370708A (en) * | 2013-08-14 | 2015-02-25 | 北京安耐吉能源工程技术有限公司 | Methyl tert-butyl ether crude product purification method and methyl tert-butyl ether production method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102827632A (en) * | 2011-06-14 | 2012-12-19 | 中国石油化工股份有限公司 | Method for processing C5 raffinate from ethene cracking |
| CN104370708A (en) * | 2013-08-14 | 2015-02-25 | 北京安耐吉能源工程技术有限公司 | Methyl tert-butyl ether crude product purification method and methyl tert-butyl ether production method |
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| CN111521721A (en) * | 2019-02-01 | 2020-08-11 | 株式会社岛津制作所 | Sulfur chemiluminescence detector |
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