CN102701969A - Etherified C4 superimposition esterification cogeneration method of isooctane and sec-butyl acetate - Google Patents
Etherified C4 superimposition esterification cogeneration method of isooctane and sec-butyl acetate Download PDFInfo
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Abstract
The invention discloses an etherified C4 superimposition esterification cogeneration method of isooctane and sec-butyl acetate. The etherified C4 superimposition esterification cogeneration method of the isooctane and the sec-butyl acetate comprises the following steps: (1), passing an etherified C4 raw material through a reactor filled with a solid acidic catalyst, performing superimposition reaction under reaction conditions that the reaction temperature is 60-90 DEG C and the pressure is 0.8-1.6MPa, and distilling a superimposition reaction product to obtain the refined C4 raw material on the top of a distillation tower and obtain C8 olefin, with iso-octene as a main part, at the bottom of the distillation tower; and (2) mixing and preheating the refined C4 raw material with acetic acid, passing the mixture through an esterification reactor filled with an esterified heteropoly acid catalyst, and reacting under reaction conditions that the temperature is 70-110 DEG C and the pressure is 1.0-1.4MPa to obtain the sec-butyl acetate. The superimposition reaction is high in selectivity; the procurement index of the C4 raw material of the sec-butyl acetate is lowered; the supply of the raw material is ensured; and the generated C8 olefin can be used as a high-octane gasoline component, thus improving the economic benefit.
Description
Technical field
The present invention relates to the production technical field of sec-butyl acetate, relate in particular to the production technology of carbon four superimposed esterification coproduction isooctenes behind a kind of ether, sec-butyl acetate.
Background technology
Along with continually developing of sec-butyl acetate new application, the consumption of sec-butyl acetate increases gradually, has driven the development of sec-butyl acetate industry, and the consumption of carbon four also increases rapidly behind its raw material MTBE.But because its catalyst development time is not very ripe than short processes; To impurity iso-butylene in the raw material require index comparatively harsh (≤0.2wt%); And the reasons such as raw material, technology and process control that adopt owing to the MTBE device; Behind the ether in the carbon four the iso-butylene massfraction generally surpass 0.25wt%, can not satisfy the requirement of producing high-quality SBA, cause sec-butyl acetate carbon four raw material sources not guarantee.
According to investigation to carbon four supply enterprise behind the 15 tame ethers, wherein only there are two tame iso-butylene content to meet the requirements, 10 tame iso-butylene content are at 0.2-2.5wt%, 3 tame iso-butylene content＞2.5wt%, major part can not satisfy the requirement of producing high-quality SBA.Therefore how reducing the iso-butylene content in carbon four raw materials behind the ether, is the bottleneck that guarantees that sec-butyl acetate is produced.
Chinese patent 00817565.9 discloses a kind of process for selective dimerisation of iso-butylene; Iso-butylene in the mixed c 4 is carried out the oligomeric beta-zeolite catalyst that comprises to be studied; And the catalyst reaction condition of its different structure studied, wherein require n-butene content≤10%wt in the mixed c 4.Wherein the n-butene of control is the main raw material of sec-butyl acetate, is more than 92% at its transformation efficiency of esterification, and selectivity is more than 98%, and therefore, this method is inappropriate for carbon four raw materials behind the ether of handling sec-butyl acetate.
Shelloil company (US2,982,799) delivers with heteropolyacid H
4SiW
12O
40-SiO
2For catalyzer with the oligomerisation method from the mixture of butene-1, iso-butylene and Trimethylmethane with the complete method of separating of iso-butylene.PhiliPs Detips company (US4,301,315) also mentions with heteropolyacid H
4SiW
12O
40-SiO
2And H
3PMo
12O
40Reach above-mentioned separation purpose as catalyzer.But when pure heteropolyacid is separated into the catalyst for oligomerization of purpose as iso-butylene and butene-1 because the acidity of catalyzer is strong excessively, the isomerizing loss of butene-1 seriously, this is quite disadvantageous for esterification.
Chinese patent CN85102831A and CN1955145A carry out modification to above-mentioned catalyzer, utilize Zn
2+, Fe
3+The isoequilibrium metals ion is to the H in the catalyzer
+Replace and make the hydrogen salt catalyzer; Reduced the loss of butene-1; But reaction product is formed complicated for the C10-C16 component; In patent, do not mention turnout in the lamination process of C4 alkene, how to control superimposed product more than the C16, and the above component boiling point of C16 exceeds gasoline boiling range scope, want strict restriction as gasoline dope.
Chinese patent CN101190860 proposes the method for a kind of C4 alkene oligomerization etherificate coproduction MTBE, isooctene and diisobutylene; Be that isooctene is illustrated wherein to the iso-butylene dimerization; Catalysts and reaction conditions are disclosed, but it requires isobutylene concentration high in the raw material, low butene-1 concentration, isobutylene concentration is 5%-100%; The weight ratio of iso-butylene and butene-1 should be higher than 1, is not suitable for to handle the micro-iso-butylene in the carbon four behind the ether.
In being directed against the open source literature and patent of acetic acid-butylene one-step synthesis sec-butyl acetate; And unexposed processing to iso-butylene in carbon four raw materials; Only have in the document to introduce and iso-butylene is partly separated when the separating butane, but its energy consumption is higher and the n-butene loss is serious through extraction rectifying method.
Summary of the invention
Technical problem to be solved by this invention is: to the deficiency of prior art existence; Providing a kind of carries out building-up reactions with four raw materials of carbon behind the ether and obtains iso-butylene content is low, n-butene content is high refining carbon four-function in producing 2-butyl acetate, the method for high octane gasoline components such as the isooctene of coproduction simultaneously.
For solving the problems of the technologies described above, technical scheme of the present invention is:
The method of carbon four superimposed esterification coproduction isooctenes, sec-butyl acetate behind the ether may further comprise the steps:
(1) building-up reactions: the reactor drum that four raw materials of carbon behind ether process is equipped with solid acid catalyst; In temperature of reaction is that 60～90 ℃, pressure are to carry out building-up reactions under the reaction conditions of 0.8～1.6Mpa; The building-up reactions product is distilled; The distillation tower top obtains refining carbon four raw materials of iso-butylene content≤0.2wt%, and obtaining at the bottom of the tower with the isooctene is main carbon eight alkene;
(2) esterification: with said refining carbon four raw materials and acetate after mixing preheating through the esterifier of esterification heteropolyacid catalyst is housed, be that 70～110 ℃, pressure are that reaction generates sec-butyl acetate under the reaction conditions of 1.0～1.4Mpa in temperature.
The process of building-up reactions is very complicated, not only has the dimerization of iso-butylene to generate 2,4; 4-trimethylammonium-1-amylene, 2; 4, the codimerization between iso-butylene and butene-1 and the butene-2 also takes place in 4-trimethylammonium-2-amylene; The dimerization of butene-2, butene-1 and codimerization between the two; Dimerisation products further generates tripolymer (C12), the tetramer (C16) with the C4 olefine reaction, the isomerization reaction between the superimposed product isomer, and under catalyst action iso-butylene and the etherification reaction of methyl alcohol generation, polymerization of divinyl or the like.
Wherein, the dipolymer 2,4 of generation, 4-2,4,4-Trimethyl-1-pentene-1,2,4,4-2,4,4-Trimethyl-1-pentene-2,2,3,3-2,4,4-Trimethyl-1-pentene, 2,3,4-2,4,4-Trimethyl-1-pentene, 3,4,4-2,4,4-Trimethyl-1-pentene octane value is all very high, is that excellent gasoline adds component; But resultant dimethyl-hexene and methyl heptene octane value are very low, need restriction; The C12 boiling point is higher in the applications as laminates, but still can be used as gasoline dope, and the boiling point of C16 exceeds the boiling range scope of gasoline, needs strict restriction.
Preferably, the iso-butylene content≤2.5wt% behind the said ether in carbon four raw materials, 1.5 times of methanol content≤iso-butylene content.The transformation efficiency that under the raw material of above composition, can guarantee n-butene is less than 10%.
Preferably, said solid acid catalyst comprises at least a in strong acidic ion resin, molecular sieve, the heteropolyacid catalyst.
Preferred as further, said strongly acidic cationic exchange resin is to exist the low suspension copolymerization to obtain polystyrene resin by vinylbenzene-Vinylstyrene at pore-creating agent, and then carries out with the vitriol oil, oleum or sulphur trioxide that sulfonation obtains; This resinoid can synthesize according to the method for well known to a person skilled in the art and obtains, also can buy from market, and be Amberlyst15/35/36 like the trade mark, Dowex50, K2611/2431, Puolite 175/275, D72/005/006, resins such as S.Said molecular sieve comprises Y series, ZSM is serial, MCM is serial or the serial molecular sieve of β; Said heteropolyacid catalyst comprises the heteropolyacid of Keggin structure, Dawson structure, Anderson structure or Silverton structure.
As preferred further, said heteropolyacid catalyst is the mixture of wolframic acid and molybdic acid and the mixture of their hydrate.
As a kind of improvement; Said building-up reactions and esterification comprise a successive building-up reactions unit and esterification unit respectively; Said building-up reactions unit comprises at least one mutual placed in-line superposition reactor, and said esterification unit comprises at least two mutual placed in-line esterifiers.
Wherein, during said building-up reactions, carbon four raw materials get into placed in-line superposition reactor by the top successively after through the preheater preheating and carry out building-up reactions behind the ether; During said esterification; Get into first reactor drum by the top after refining carbon four raw materials and acetate and the two sections recycle stock mixing preheatings and carry out one section esterification; Get into second reactor drum from the top after one section esterification products and the refining carbon four raw materials mix preheatings of adding and carry out two sections esterifications; Two sections esterification products parts go to utilize rectifying tower that mixture separation is purified, and refining separation obtains the product sec-butyl acetate, and another part goes to participate in one section esterification as recycle stock.
Operating method superimposed, esterification of the present invention can be periodical operation or operate continuously, preferred operate continuously, and reactor types can be selected fixed-bed reactor, shell and tube reactor, adiabatic reactor, flowing bed reactor, tower reactor etc.
Preferably, the molar ratio of acetate and refining carbon four is 2～4 in the said esterification.
Preferably, the charging air speed of said building-up reactions is 0.2～20h
-1, the charging air speed of said esterification is 0.5-3h
-1
Preferred as further, the charging air speed of said building-up reactions is 0.5～1.2h
-1, the charging air speed of said esterification is 0.5-1h
-1
Owing to adopted technique scheme, the invention has the beneficial effects as follows:
1, the present invention with ether after carbon four under certain temperature and pressure; Through the bed of special solid acid catalyst is housed, make a small amount of iso-butylene wherein carry out selective dimerisation, dimerization reaction, be converted into carbon eight alkene; Through the method for rectifying it is separated again; Simultaneously can part divinyl and amylene be converted into polymkeric substance, its part is removed, carbon four raw materials that obtain iso-butylene content≤0.2wt% are participated in esterification; Thereafter, n-butene in carbon four raw materials and acetate react catalytic Synthesis of sec-Butyl Acetate under certain temperature, pressure condition under the effect of esterification heteropolyacid catalyst.The present invention passes through to adopt reaction conditionss such as rational temperature, pressure, and selects suitable polymerization catalyst for use, and iso-butylene and the methanol content in carbon four raw materials behind the control ether; Isobutene conversion when making building-up reactions can reach more than 94%; Butadiene conversion reaches more than 60%, and the n-butene loss is below 6%, and selectivity reaches more than 98%; But coproduction simultaneously is main carbon eight alkene with the isooctene, and carbon eight alkene can be used as gasoline dope and use.The present invention has not only reduced the buying index of sec-butyl acetate material carbon four, has enlarged purchasing of raw materials scope, has guaranteed raw material supply, and simultaneously, carbon eight alkene of generation can be used as high octane gasoline component, have improved economic benefit.
2, the solid acid catalyst that uses during building-up reactions of the present invention comprises at least a in strong acidic ion resin, molecular sieve, the heteropolyacid catalyst; Wherein heteropolyacid catalyst is the mixture of wolframic acid and molybdic acid and the mixture of their hydrate; Use the good polymerization catalyst of catalytic performance, so the selectivity of building-up reactions is strong, isobutene conversion is high; The n-butene loss is low, has satisfied the requirement of producing high-quality SBA.
3, building-up reactions of the present invention and esterification comprise a successive building-up reactions unit and esterification unit respectively; Wherein the building-up reactions unit comprises at least one mutual placed in-line superposition reactor, and the esterification unit comprises at least two mutual placed in-line esterifiers.During building-up reactions, get into placed in-line superposition reactor by the top successively after the preheating of carbon four raw materials process preheater behind the ether and carry out building-up reactions; During said esterification; Get into first reactor drum by the top after refining carbon four raw materials and acetate and the two sections recycle stock mixing preheatings and carry out one section esterification; Get into second reactor drum from the top after one section esterification products and the surplus preheating of adding of refining carbon four raw materials mix and carry out two sections esterifications; Two sections esterification products parts go to utilize rectifying tower that mixture separation is purified; Refining separation obtains the product sec-butyl acetate, and another part goes to participate in one section esterification as recycle stock, reaction of high order improved superimposed and esterification reaction conversion ratio guaranteed reaction effect.
Embodiment
Below in conjunction with concrete embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.Should be understood that in addition those skilled in the art can do various changes or modification to the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
(1) building-up reactions: with iso-butylene content 2.0wt%; Carbon four raw materials are through being equipped with the reactor drum of Amberlyst 15 resin catalysts behind 1.5 times the ether of methanol content≤iso-butylene content; In temperature of reaction is that 66 ℃, pressure are to carry out building-up reactions under the reaction conditions of 1.6Mpa; The building-up reactions product is distilled, and the distillation tower top obtains refining carbon four raw materials of iso-butylene content≤0.0945wt%, and obtaining at the bottom of the tower with the isooctene is main carbon eight alkene;
(2) esterification: with said refining carbon four raw materials and acetate after mixing preheating through the esterifier of esterification heteropolyacid catalyst is housed, be that 75 ℃, pressure are that reaction generates sec-butyl acetate under the reaction conditions of 1.4Mpa in temperature.
Embodiment 2
(1) building-up reactions: through the reactor drum of Y catalyst series is housed, is that 90 ℃, pressure be the reaction conditions of 0.8Mpa under carry out building-up reactions in temperature of reaction with four raw materials of carbon behind the ether, and the charging air speed of building-up reactions is 1.0h
-1, the building-up reactions product to be distilled, the distillation tower top obtains refining carbon four raw materials of iso-butylene content 0.0744wt%, and obtaining at the bottom of the tower with the isooctene is main carbon eight alkene;
(2) esterification: with said refining carbon four raw materials and acetate after mixing preheating through the esterifier of esterification heteropolyacid catalyst is housed, the molar ratio of acetate and refining carbon four is 3, the charging air speed of esterification is 0.8h
-1, be that 110 ℃, pressure are that reaction generates sec-butyl acetate under the reaction conditions of 1.0Mpa in temperature.
Embodiment 3
(1) building-up reactions: with iso-butylene content 2.4wt%; Carbon four raw materials are through the reactor drum of the heteropolyacid catalyst of the Keggin structure of mixture composition that wolframic acid and molybdic acid are housed behind 1.5 times the ether of methanol content≤iso-butylene content; In temperature of reaction is that 80 ℃, pressure are to carry out building-up reactions under the reaction conditions of 1.2Mpa; The building-up reactions product is distilled, and the distillation tower top obtains refining carbon four raw materials of iso-butylene content 0.0984wt%, and obtaining at the bottom of the tower with the isooctene is main carbon eight alkene;
(2) esterification: with said refining carbon four raw materials and acetate after mixing preheating through the esterifier of esterification heteropolyacid catalyst is housed; The molar ratio of acetate and refining carbon four is 2.5, is that 90 ℃, pressure are that reaction generates sec-butyl acetate under the reaction conditions of 1.2Mpa in temperature.
Embodiment 4
(1) building-up reactions: with iso-butylene content 2.5wt%; Carbon four raw materials are through the reactor drum of heteropolyacid catalyst of the Silverton structure of mixture that wolframic acid and molybdic acid are housed behind 1.5 times the ether of methanol content≤iso-butylene content, and the charging air speed of building-up reactions is 0.6h
-1, be that 75 ℃, pressure are to carry out building-up reactions under the reaction conditions of 1.1Mpa in temperature of reaction, the building-up reactions product to be distilled, the distillation tower top obtains refining carbon four raw materials of iso-butylene content 0.0986wt%, and obtaining at the bottom of the tower with the isooctene is main carbon eight alkene;
(2) esterification: adopt the secondary continuous esterification during esterification, the molar ratio of acetate and refining carbon four is 3, and the charging air speed is 0.7h
-1Get into first reactor drum by the top after refining carbon four raw materials and acetate and the two sections recycle stock mixing preheatings and carry out one section esterification; Get into second reactor drum from the top after one section esterification products and the surplus preheating of adding of refining carbon four raw materials mix and carry out two sections esterifications; Two sections esterification products parts go to utilize rectifying tower that mixture separation is purified, and refining separation obtains the product sec-butyl acetate, and another part goes to participate in one section esterification as recycle stock.The two-stage esterification reaction temperature be respectively 85 ℃, pressure be 1.15Mpa reaction conditions down reaction generate sec-butyl acetate.
Embodiment 5
(1) building-up reactions: building-up reactions adopts the continuous building-up reactions of two-stage; With iso-butylene content 2.15wt%; Get into the superposition reactor of two-stage series connection of heteropolyacid of the mixture D awson structure of the hydrate that wolframic acid and molybdic acid are housed behind 1.5 times the ether of methanol content≤iso-butylene content after the carbon four feed preheater preheatings successively by the top; Carry out building-up reactions successively, temperature of reaction is that 85 ℃, pressure are to carry out building-up reactions under the reaction conditions of 0.95Mpa, and the building-up reactions product is distilled; The distillation tower top obtains refining carbon four raw materials of iso-butylene content 0.0970wt%, and obtaining at the bottom of the tower with the isooctene is main carbon eight olefin gasolines;
(2) esterification: adopt the secondary continuous esterification during esterification, the molar ratio of acetate and refining carbon four is 3.5, and the charging air speed is 0.9h
-1Get into first reactor drum by the top after refining carbon four raw materials and acetate and the two sections recycle stock mixing preheatings and carry out one section esterification; Get into second reactor drum from the top after one section esterification products and the surplus preheating of adding of refining carbon four raw materials mix and carry out two sections esterifications; Two sections esterification products parts are gone to make with extra care to separate and are obtained the product sec-butyl acetate, and another part goes to participate in one section esterification as recycle stock.The two-stage esterification reaction temperature be respectively 105 ℃, pressure be 1.3Mpa reaction conditions down reaction generate sec-butyl acetate.
The raw material index of carbon four is seen table 1 behind the ether that embodiment 1 to embodiment 5 uses, and the quality index situation of refining carbon four, polymer gasoline and the esterification products of embodiment 1 to embodiment 5 preparation is seen table 2, table 3 and table 4 respectively.
Table 1
Table 2
| Form | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Propane (wt%) | 0.0525 | 0.0331 | 0.1785 | 0.0035 | 0.0014 |
| Propylene (wt%) | 0.0105 | 0.0050 | 0.0514 | 0.0007 | 0.0005 |
| Trimethylmethane (wt%) | 33.0556 | 32.5093 | 32.4871 | 33.9171 | 32.3274 |
| Normal butane (wt%) | 18.2954 | 21.2657 | 20.5581 | 17.5774 | 19.1865 |
| Anti-butylene (wt%) | 25.6045 | 25.9287 | 25.1315 | 25.2287 | 27.1537 |
| N-butene (wt%) | 8.9998 | 8.5172 | 8.9960 | 9.9064 | 8.9613 |
| Iso-butylene (wt%) | 0.0945 | 0.0744 | 0.0984 | 0.0986 | 0.0970 |
| Maleic (wt%) | 13.8007 | 11.5981 | 12.0647 | 13.2170 | 11.8843 |
| Divinyl (wt%) | 0.0840 | 0.0663 | 0.4311 | 0.0495 | 0.3857 |
| Iso-pentane (wt%) | 0.0025 | 0.0022 | 0.0032 | 0.0012 | 0.0022 |
| Isopentene (wt%) | Trace | Trace | Trace | Trace | Trace |
Table 3
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Outward appearance | Colourless liquid | Weak yellow liquid | Colourless liquid | Weak yellow liquid | Weak yellow liquid |
| Density (40 ℃) kg/m | 703 | 704 | 702 | 703 | 704 |
| Viscosity cP | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Boiling range ℃ | 40～200 | 40～200 | 40～200 | 40～200 | 40～200 |
| Octane value (RON) | ≥95 | ≥95 | ≥95 | ≥95 | ≥95 |
| Form | %(m) | %(m) | %(m) | %(m) | %(m) |
| C5～C7 hydrocarbon | 13.0 | 13.4 | 12.8 | 13.1 | 13.4 |
| The C8 hydrocarbon | 75.0 | 75.1 | 74.7 | 74.6 | 75.3 |
| C9～C11 hydrocarbon | 4.7 | 3.6 | 5.2 | 4.2 | 3.4 |
| The C12+ hydrocarbon | 7.3 | 7.9 | 7.3 | 8.1 | 7.9 |
Table 4
| Form | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Propane (wt%) | 0.025 | 0.012 | 0.005 | 0.000 | 0.000 |
| Trimethylmethane (wt%) | 15.741 | 15.571 | 15.732 | 15.978 | 15.476 |
| Normal butane (wt%) | 8.451 | 10.084 | 9.826 | 8.032 | 9.093 |
| Anti-butylene (wt%) | 3.048 | 4.221 | 4.241 | 4.174 | 4.548 |
| N-butene (wt%) | 0.214 | 0.195 | 0.220 | 0.099 | 0.189 |
| Iso-butylene (wt%) | Trace | Trace | Trace | Trace | Trace |
| Maleic (wt%) | 0.986 | 0.779 | 0.884 | 1.012 | 0.990 |
| Acetate (wt%) | 30.208 | 30.432 | 29.056 | 29.874 | 30.536 |
| Sec-butyl acetate (wt%) | 39.343 | 37.408 | 39.089 | 38.328 | 38.314 |
| Other (wt%) | 1.984 | 1.298 | 0.947 | 2.503 | 0.854 |
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; The present invention is not restricted to the described embodiments; That describes in the foregoing description and the specification sheets just explains principle of the present invention; Under the prerequisite that does not break away from spirit and scope of the invention, the present invention also has various changes and modifications, and these variations and improvement all fall in the scope of the invention that requires protection.The present invention requires protection domain to be defined by appending claims and equivalent thereof.
All are from design of the present invention, and the structural transformation of having done without creative work all drops within protection scope of the present invention.
Claims (10)
1. the method for carbon four superimposed esterification coproduction isooctenes, sec-butyl acetate behind the ether is characterized in that may further comprise the steps:
(1) building-up reactions: the reactor drum that four raw materials of carbon behind ether process is equipped with solid acid catalyst; In temperature of reaction is that 60～90 ℃, pressure are to carry out building-up reactions under the reaction conditions of 0.8～1.6Mpa; The building-up reactions product is distilled; The distillation tower top obtains refining carbon four raw materials of iso-butylene content≤0.2wt%, obtains isooctene at the bottom of the tower;
(2) esterification: with said refining carbon four raw materials and acetate after mixing preheating through the esterifier of esterification heteropolyacid catalyst is housed, be that 70～110 ℃, pressure are that reaction generates sec-butyl acetate under the reaction conditions of 1.0～1.4Mpa in temperature.
2. the method for carbon four superimposed esterification coproduction isooctenes, sec-butyl acetate behind the ether as claimed in claim 1 is characterized in that: the iso-butylene content≤2.5wt% behind the said ether in carbon four raw materials, 1.5 times of methanol content≤iso-butylene content.
3. the method for carbon four superimposed esterification coproduction isooctenes, sec-butyl acetate behind the ether as claimed in claim 1 is characterized in that: said solid acid catalyst comprises at least a in strong acidic ion resin, molecular sieve, the heteropolyacid catalyst.
4. the method for carbon four superimposed esterification coproduction isooctenes, sec-butyl acetate behind the ether as claimed in claim 3; It is characterized in that: said strongly acidic cationic exchange resin is to exist the low suspension copolymerization to obtain polystyrene resin by vinylbenzene-Vinylstyrene at pore-creating agent, and then carries out with the vitriol oil, oleum or sulphur trioxide that sulfonation obtains; Said molecular sieve comprises Y series, ZSM is serial, MCM is serial or the serial molecular sieve of β; Said heteropolyacid catalyst comprises the heteropolyacid of Keggin structure, Dawson structure, Anderson structure or Silverton structure.
5. the method for carbon four superimposed esterification coproduction isooctenes, sec-butyl acetate behind the ether as claimed in claim 4, it is characterized in that: said heteropolyacid catalyst is the mixture of wolframic acid and molybdic acid and the mixture of their hydrate.
6. like the method for the four superimposed esterification coproduction isooctenes of carbon behind described any ether of claim 1 to 5, sec-butyl acetate; It is characterized in that: said building-up reactions and esterification comprise a successive building-up reactions unit and esterification unit respectively; Said building-up reactions unit comprises at least one mutual placed in-line superposition reactor, and said esterification unit comprises at least two mutual placed in-line esterifiers.
7. the method for carbon four superimposed esterification coproduction isooctenes, sec-butyl acetate behind the ether as claimed in claim 6; It is characterized in that: during said esterification; Get into first reactor drum by the top after refining carbon four raw materials and acetate and the two sections recycle stock mixing preheatings and carry out one section esterification; Get into second reactor drum from the top after one section esterification products and the refining carbon four raw materials mix preheatings of adding and carry out two sections esterifications; Two sections esterification products parts are gone to make with extra care to separate and are obtained the product sec-butyl acetate, and another part goes to participate in one section esterification as recycle stock.
8. the method for carbon four superimposed esterification coproduction isooctenes, sec-butyl acetate behind the ether as claimed in claim 6, it is characterized in that: the molar ratio of acetate and refining carbon four is 2～4 in the said esterification.
9. the method for carbon four superimposed esterification coproduction isooctenes, sec-butyl acetate behind the ether as claimed in claim 6, it is characterized in that: the charging air speed of said building-up reactions is 0.2～20h
-1, the charging air speed of said esterification is 0.5-3h
-1
10. the method for carbon four superimposed esterification coproduction isooctenes, sec-butyl acetate behind the ether as claimed in claim 9,, it is characterized in that: the charging air speed of said building-up reactions is 0.5～1.2h
-1, the charging air speed of said esterification is 0.5-1h
-1
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Cited By (9)
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|---|---|---|---|---|
| CN102964243A (en) * | 2012-11-16 | 2013-03-13 | 北京石油化工学院 | Preparation method of sec-butyl acetate |
| CN103657720A (en) * | 2013-12-10 | 2014-03-26 | 王金明 | Post-ether carbon-four polymerized catalyst as well as preparation method and application thereof |
| CN107954816A (en) * | 2017-12-23 | 2018-04-24 | 天津海成能源工程技术有限公司 | Isobutene, the method for butadiene in a kind of removing mixing carbon four |
| CN109232156A (en) * | 2017-07-11 | 2019-01-18 | 湖南中创化工股份有限公司 | A method of preparing iso-amylene |
| CN112341303A (en) * | 2019-08-07 | 2021-02-09 | 中国石油化工股份有限公司 | Method for reducing 1-butene loss in cracking carbon four selective polymerization process |
| CN113582801A (en) * | 2020-04-30 | 2021-11-02 | 中国石油化工股份有限公司 | Process for preparing isooctene by selective superposition of mixed C4 |
| CN113582799A (en) * | 2020-04-30 | 2021-11-02 | 中国石油化工股份有限公司 | Method for preparing isooctene by selective polymerization of mixed C4 with low 1-butene loss |
| CN114436850A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Method for co-producing monoethylamine and sec-butylamine by supergravity method |
| CN114763314A (en) * | 2021-01-11 | 2022-07-19 | 中国石油天然气股份有限公司 | Mixed C4 hydrocarbon polymerization process and polymerization resin catalyst |
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Cited By (13)
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| CN102964243B (en) * | 2012-11-16 | 2017-07-11 | 北京石油化工学院 | The preparation method of sec-Butyl Acetate |
| CN102964243A (en) * | 2012-11-16 | 2013-03-13 | 北京石油化工学院 | Preparation method of sec-butyl acetate |
| CN103657720A (en) * | 2013-12-10 | 2014-03-26 | 王金明 | Post-ether carbon-four polymerized catalyst as well as preparation method and application thereof |
| CN109232156B (en) * | 2017-07-11 | 2022-03-04 | 湖南中创化工股份有限公司 | Method for preparing isoamylene |
| CN109232156A (en) * | 2017-07-11 | 2019-01-18 | 湖南中创化工股份有限公司 | A method of preparing iso-amylene |
| CN107954816A (en) * | 2017-12-23 | 2018-04-24 | 天津海成能源工程技术有限公司 | Isobutene, the method for butadiene in a kind of removing mixing carbon four |
| CN112341303A (en) * | 2019-08-07 | 2021-02-09 | 中国石油化工股份有限公司 | Method for reducing 1-butene loss in cracking carbon four selective polymerization process |
| CN113582801A (en) * | 2020-04-30 | 2021-11-02 | 中国石油化工股份有限公司 | Process for preparing isooctene by selective superposition of mixed C4 |
| CN113582799A (en) * | 2020-04-30 | 2021-11-02 | 中国石油化工股份有限公司 | Method for preparing isooctene by selective polymerization of mixed C4 with low 1-butene loss |
| CN113582799B (en) * | 2020-04-30 | 2023-09-05 | 中国石油化工股份有限公司 | Method for preparing isooctene by mixed carbon four-selectivity superposition with low 1-butene loss |
| CN113582801B (en) * | 2020-04-30 | 2023-09-05 | 中国石油化工股份有限公司 | Process for preparing isooctenes by mixing carbon four selective overlapping |
| CN114436850A (en) * | 2020-11-02 | 2022-05-06 | 中国石油化工股份有限公司 | Method for co-producing monoethylamine and sec-butylamine by supergravity method |
| CN114763314A (en) * | 2021-01-11 | 2022-07-19 | 中国石油天然气股份有限公司 | Mixed C4 hydrocarbon polymerization process and polymerization resin catalyst |
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