CN102701969B - 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 the superimposed esterification coproduction of carbon four isooctene after 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 after its raw material MTBE, the consumption of carbon four also increases rapidly.But because its catalyst development time is not very ripe compared with short processes, impurity iso-butylene in raw material required to index comparatively harsh (≤0.2wt%), and the reason such as raw material, technique and process control adopting due to MTBE device, after ether, in carbon four, iso-butylene massfraction generally exceedes 0.25wt%, can not meet the requirement of production high-quality SBA, cause sec-butyl acetate carbon four raw material sources not guarantee.
According to the investigation to carbon four supply enterprise after 15 ethers, wherein only there are two iso-butylene content to meet the requirements, 10 iso-butylene content are at 0.2-2.5wt%, 3 iso-butylene content > 2.5wt%, and major part can not meet the requirement of production high-quality SBA.Therefore how reducing the iso-butylene content in carbon four raw materials after 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 mixed c 4 is carried out to the oligomeric beta-zeolite catalyst that comprises to be studied, and the catalyst reaction condition of its different structure is studied, wherein require n-butene content≤10%wt in mixed c 4.The n-butene of wherein the controlling main raw material that is sec-butyl acetate, is more than 92% at its transformation efficiency of esterification, and selectivity is more than 98%, and therefore, this method is unsuitable for processing carbon four raw materials after the ether of sec-butyl acetate.
Shelloil company (US2,982,799) delivers with heteropolyacid H
4siW
12o
40-SiO
2the method of iso-butylene being separated completely from the mixture of butene-1, iso-butylene and Trimethylmethane by oligomerisation method for catalyzer.PhiliPs Detips company (US4,301,315) also mentions with heteropolyacid H
4siW
12o
40-SiO
2and H
3pMo
12o
40as catalyzer, reach above-mentioned separation object.But when pure heteropolyacid is separated into the catalyst for oligomerization of object as iso-butylene and butene-1, because the acidity of catalyzer is excessively strong, the isomerization loss of butene-1 is serious, and this is quite disadvantageous for esterification.
Chinese patent CN85102831A and CN1955145A carry out modification to above-mentioned catalyzer, utilize Zn
2+, Fe
3+isoequilibrium metal ion is to the H in catalyzer
+replace and make acid salt catalyzer, reduced the loss of butene-1, but reaction product is that C10-C16 component composition is complicated, in patent, do not mention turnout how to control more than C16 superimposed product in the lamination process of C4 alkene, and the above component boiling point of C16 exceeds gasoline boiling range scope, as gasoline dope, to strictly limit.
Chinese patent CN101190860 proposes a kind of method of C4 alkene oligomerization etherificate coproduction MTBE, isooctene and diisobutylene, to iso-butylene dimerization, be wherein that isooctene is illustrated, catalysts and reaction conditions are disclosed, but it requires isobutylene concentration high in 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 and processes the micro-iso-butylene in carbon four after ether.
In open source literature and patent for acetic acid-butylene one-step synthesis sec-butyl acetate, and the unexposed processing for iso-butylene in carbon four raw materials, only have in document to introduce by extraction rectifying method iso-butylene part to be separated when the separating butane, but its energy consumption is higher and n-butene loss is serious.
Summary of the invention
Technical problem to be solved by this invention is: the deficiency existing for prior art, providing a kind of carries out building-up reactions by four raw materials of carbon after ether and obtains iso-butylene content is low, n-butene content is high refining carbon four for the production of 2-butyl acetate, the method for the 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 the superimposed esterification coproduction of carbon four isooctene, sec-butyl acetate after ether, comprises the following steps:
(1) building-up reactions: the reactor that the four raw materials processes of carbon after ether is equipped with to solid acid catalyst, in temperature of reaction, be to carry out building-up reactions under 60～90 ℃, the pressure reaction conditions that is 0.8～1.6Mpa, building-up reactions product is distilled, distillation tower top obtains refining carbon four raw materials of iso-butylene content≤0.2wt%, obtains take isooctene as main carbon eight alkene at the bottom of tower;
(2) esterification: by described refining carbon four raw materials and acetic acid after mixing preheating through the esterifier of esterification heteropolyacid catalyst being housed, in temperature, be that under 70～110 ℃, the pressure reaction conditions that is 1.0～1.4Mpa, reaction generates sec-butyl acetate.
The process of building-up reactions is very complicated, not only there is the dimerization of iso-butylene to generate 2,4,4-trimethylammonium-1-amylene, 2,4,4-trimethylammonium-2-amylene, also there is the codimerization between iso-butylene and butene-1 and butene-2, the dimerization of butene-2, butene-1 and codimerization between the two, dimerisation products further generates tripolymer (C12), the tetramer (C16) with C4 olefine reaction, isomerization reaction between superimposed product isomer, and etherification reaction that iso-butylene and methyl alcohol occur under catalyst action, the polymerization of divinyl etc.
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; In applications as laminates, C12 boiling point is higher, but still can be used as gasoline dope, and the boiling point of C16 exceeds the boiling range scope of gasoline, need strictly limit.
Preferably, the iso-butylene content≤2.5wt% after described ether in carbon four raw materials, 1.5 times of methanol content≤iso-butylene content.Under the raw material of above composition, can guarantee that the transformation efficiency of n-butene is less than 10%.
Preferably, described solid acid catalyst comprises at least one in strong acidic ion resin, molecular sieve, heteropolyacid catalyst.
As further preferably, described storng-acid cation exchange resin is at pore-creating agent, to exist low suspension copolymerization to obtain polystyrene resin by styrene-divinylbenzene, and then with the vitriol oil, oleum or sulphur trioxide, carries out that sulfonation obtains; This resinoid can synthesize and obtain according to the method for well known to a person skilled in the art, also can buy from market, and if the trade mark is Amberlyst15/35/36, Dowex50, K2611/2431, Puolite 175/275, D72/005/006, the resins such as S.Described molecular sieve comprises Y-series, ZSM series, MCM series or β Series Molecules sieve; Described heteropolyacid catalyst comprises the heteropolyacid of Keggin structure, Dawson structure, Anderson structure or Silverton structure.
As further preferably, described heteropolyacid catalyst is the mixture of wolframic acid and molybdic acid and the mixture of their hydrate.
As one, improve, described building-up reactions and esterification comprise respectively a continuous building-up reactions unit and esterification unit, described building-up reactions unit comprises the superposition reactor that at least one is connected mutually, and described esterification unit comprises at least two esterifiers of series connection mutually.
Wherein, during described building-up reactions, the superposition reactor that after ether, carbon four raw materials enter series connection by top successively after preheater preheating carries out building-up reactions; During described esterification, refining carbon four raw materials with after acetic acid and two sections of recycle stock mixing preheatings, by top, enter the first reactor and carry out one section of esterification, one section of esterification products with after the refining carbon four raw material mixing preheatings of adding, from top, enter the second reactor and carry out two sections of esterifications, two sections of esterification products parts go to utilize rectifying tower to purify to mixture separation, refining separation obtains product sec-butyl acetate, and another part goes to participate in one section of esterification as recycle stock.
Operating method superimposed, esterification of the present invention can be periodical operation or operate continuously, preferably operate continuously, and reactor types can be selected fixed-bed reactor, shell and tube reactor, adiabatic reactor, flowing bed reactor, tower reactor etc.
Preferably, in described esterification, the molar ratio of acetic acid and refining carbon four is 2～4.
Preferably, the charging air speed of described building-up reactions is 0.2～20h
-1, the charging air speed of described esterification is 0.5-3h
-1.
As further preferred, the charging air speed of described building-up reactions is 0.5～1.2h
-1, the charging air speed of described esterification is 0.5-1h
-1.
Owing to having adopted technique scheme, the invention has the beneficial effects as follows:
1, the present invention by carbon after ether four under certain temperature and pressure, by 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, by the method for rectifying, be isolated again, part divinyl and amylene can be converted into polymkeric substance, its part is removed, carbon four raw materials that obtain iso-butylene content≤0.2wt% are participated in esterification simultaneously; Thereafter, the n-butene in carbon four raw materials and acetic acid, under the effect of esterification heteropolyacid catalyst, react catalytic Synthesis of sec-Butyl Acetate under certain temperature, pressure condition.The present invention is by adopting the reaction conditionss such as rational temperature, pressure, and select suitable polymerization catalyst, and control iso-butylene and the methanol content in carbon four raw materials after ether, isobutene conversion while making building-up reactions can reach more than 94%, butadiene conversion reaches more than 60%, and n-butene loss is below 6%, and selectivity reaches more than 98%, simultaneously can coproduction take isooctene as main carbon eight alkene, 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 expanded purchasing of raw materials scope, has guaranteed raw material supply, and meanwhile, carbon eight alkene of generation can be used as high octane gasoline component, have improved economic benefit.
2, the solid acid catalyst using during building-up reactions of the present invention comprises at least one in strong acidic ion resin, molecular sieve, 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, therefore the selectivity of building-up reactions is strong, isobutene conversion is high, n-butene loss is low, has met the requirement of production high-quality SBA.
3, building-up reactions of the present invention and esterification comprise respectively a continuous building-up reactions unit and esterification unit, wherein building-up reactions unit comprises the superposition reactor that at least one is connected mutually, and esterification unit comprises at least two esterifiers of series connection mutually.During building-up reactions, the superposition reactor that after ether, carbon four raw materials enter series connection by top successively after preheater preheating carries out building-up reactions, during described esterification, refining carbon four raw materials with after acetic acid and two sections of recycle stock mixing preheatings, by top, enter the first reactor and carry out one section of esterification, more than one section of esterification products mixes with refining carbon four raw materials of adding, after preheating, from top, enter the second reactor and carry out two sections of esterifications, two sections of esterification products parts go to utilize rectifying tower to purify to mixture separation, refining separation obtains product sec-butyl acetate, another part goes to participate in one section of esterification as recycle stock, reaction of high order improved superimposed and esterification reaction conversion ratio guaranteed reaction effect.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
(1) building-up reactions: by iso-butylene content 2.0wt%, after the ether of 1.5 times of methanol content≤iso-butylene content, carbon four raw materials are through being equipped with the reactor of Amberlyst 15 resin catalysts, in temperature of reaction, be to carry out building-up reactions under 66 ℃, the pressure reaction conditions that is 1.6Mpa, building-up reactions product is distilled, distillation tower top obtains refining carbon four raw materials of iso-butylene content≤0.0945wt%, obtains take isooctene as main carbon eight alkene at the bottom of tower;
(2) esterification: by described refining carbon four raw materials and acetic acid after mixing preheating through the esterifier of esterification heteropolyacid catalyst being housed, in temperature, be that under 75 ℃, the pressure reaction conditions that is 1.4Mpa, reaction generates sec-butyl acetate.
Embodiment 2
(1) building-up reactions: through the reactor of Y-series catalyzer is housed, be 90 ℃, pressure be 0.8Mpa reaction conditions under to carry out building-up reactions in temperature of reaction by four raw materials of carbon after ether, the charging air speed of building-up reactions is 1.0h
-1, building-up reactions product to be distilled, distillation tower top obtains refining carbon four raw materials of iso-butylene content 0.0744wt%, obtains take isooctene as main carbon eight alkene at the bottom of tower;
(2) esterification: by described refining carbon four raw materials and acetic acid after mixing preheating through the esterifier of esterification heteropolyacid catalyst is housed, the molar ratio of acetic acid and refining carbon four is 3, the charging air speed of esterification is 0.8h
-1, in temperature, be that under 110 ℃, the pressure reaction conditions that is 1.0Mpa, reaction generates sec-butyl acetate.
Embodiment 3
(1) building-up reactions: by iso-butylene content 2.4wt%, after the ether of 1.5 times of methanol content≤iso-butylene content, carbon four raw materials processes are equipped with the reactor of the heteropolyacid catalyst of the Keggin structure of the compositions of mixtures of wolframic acid and molybdic acid, in temperature of reaction, be to carry out building-up reactions under 80 ℃, the pressure reaction conditions that is 1.2Mpa, building-up reactions product is distilled, distillation tower top obtains refining carbon four raw materials of iso-butylene content 0.0984wt%, obtains take isooctene as main carbon eight alkene at the bottom of tower;
(2) esterification: by described refining carbon four raw materials and acetic acid after mixing preheating through the esterifier of esterification heteropolyacid catalyst is housed, the molar ratio of acetic acid and refining carbon four is 2.5, in temperature, is that under 90 ℃, the pressure reaction conditions that is 1.2Mpa, reaction generates sec-butyl acetate.
Embodiment 4
(1) building-up reactions: by iso-butylene content 2.5wt%, after the ether of 1.5 times of methanol content≤iso-butylene content, carbon four raw materials processes are equipped with the reactor of the heteropolyacid catalyst of the Silverton structure of the mixture of wolframic acid and molybdic acid, and the charging air speed of building-up reactions is 0.6h
-1, in temperature of reaction, be to carry out building-up reactions under 75 ℃, the pressure reaction conditions that is 1.1Mpa, building-up reactions product to be distilled, distillation tower top obtains refining carbon four raw materials of iso-butylene content 0.0986wt%, obtains take isooctene as main carbon eight alkene at the bottom of tower;
(2) esterification: adopt secondary continuous esterification during esterification, the molar ratio of acetic acid and refining carbon four is 3, and charging air speed is 0.7h
-1refining carbon four raw materials with after acetic acid and two sections of recycle stock mixing preheatings, by top, enter the first reactor and carry out one section of esterification, more than one section of esterification products mixes with refining carbon four raw materials of adding, after preheating, from top, enter the second reactor and carry out two sections of esterifications, two sections of esterification products parts go to utilize rectifying tower to purify to mixture separation, refining separation obtains product sec-butyl acetate, and another part goes to participate in one section of esterification as recycle stock.Two-stage esterification reaction temperature is respectively reaction under the reaction conditions that 85 ℃, pressure are 1.15Mpa and generates sec-butyl acetate.
Embodiment 5
(1) building-up reactions: building-up reactions adopts the continuous building-up reactions of two-stage, by iso-butylene content 2.15wt%, after the ether of 1.5 times of methanol content≤iso-butylene content, after carbon four feed preheater preheatings, by top, entered successively the superposition reactor of the two-stage series connection of the heteropolyacid of the mixture D awson structure of the hydrate that wolframic acid and molybdic acid are housed, carry out successively building-up reactions, temperature of reaction is 85 ℃, pressure is to carry out building-up reactions under the reaction conditions of 0.95Mpa, building-up reactions product is distilled, distillation tower top obtains refining carbon four raw materials of iso-butylene content 0.0970wt%, at the bottom of tower, obtain take isooctene as main carbon eight olefin gasolines,
(2) esterification: adopt secondary continuous esterification during esterification, the molar ratio of acetic acid and refining carbon four is 3.5, and charging air speed is 0.9h
-1refining carbon four raw materials with after acetic acid and two sections of recycle stock mixing preheatings, by top, enter the first reactor and carry out one section of esterification, more than one section of esterification products mixes with refining carbon four raw materials of adding, after preheating, from top, enter the second reactor and carry out two sections of esterifications, two sections of esterification products parts are gone to refine to separate and are obtained product sec-butyl acetate, and another part goes to participate in one section of esterification as recycle stock.Two-stage esterification reaction temperature is respectively reaction under the reaction conditions that 105 ℃, pressure are 1.3Mpa and generates sec-butyl acetate.
The quality index situation of refining carbon four, polymer gasoline and esterification products that after the ether that embodiment 1 to embodiment 5 is used, the raw material index of carbon four is prepared in Table 1, embodiment 1 to embodiment 5 respectively in Table 2, table 3 and table 4.
Table 1
Table 2
| Composition | 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 |
| Composition | %(m) | %(m) | %(m) | %(m) | %(m) |
| C5～C7 hydrocarbon | 13.0 | 13.4 | 12.8 | 13.1 | 13.4 |
| 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 |
| C12+ hydrocarbon | 7.3 | 7.9 | 7.3 | 8.1 | 7.9 |
Table 4
| Composition | 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 |
| Acetic acid (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 in above-described embodiment and specification sheets, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
All from the present invention is to devise, within the structural transformation of having done without creative work all drops on protection scope of the present invention.
Claims (8)
1. the method for the superimposed esterification coproduction of carbon four isooctene, sec-butyl acetate after ether, is characterized in that comprising the following steps:
(1) building-up reactions: the reactor that the four raw materials processes of carbon after ether is equipped with to solid acid catalyst, in temperature of reaction, be to carry out building-up reactions under 60～90 ℃, the pressure reaction conditions that is 0.8～1.6Mpa, building-up reactions product is distilled, distillation tower top obtains refining carbon four raw materials of iso-butylene content≤0.2wt%, obtains isooctene at the bottom of tower;
(2) esterification: by described refining carbon four raw materials and acetic acid after mixing preheating through the esterifier of esterification heteropolyacid catalyst being housed, in temperature, be that under 70～110 ℃, the pressure reaction conditions that is 1.0～1.4Mpa, reaction generates sec-butyl acetate;
Described building-up reactions and esterification comprise respectively a continuous building-up reactions unit and esterification unit, described building-up reactions unit comprises the superposition reactor that at least one is connected mutually, and described esterification unit comprises at least two esterifiers of series connection mutually; During described esterification, refining carbon four raw materials with after acetic acid and two sections of recycle stock mixing preheatings, by top, enter the first reactor and carry out one section of esterification, one section of esterification products with after the refining carbon four raw material mixing preheatings of adding, from top, enter the second reactor and carry out two sections of esterifications, two sections of esterification products parts are gone to refine to separate and are obtained product sec-butyl acetate, and another part goes to participate in one section of esterification as recycle stock.
2. the method for the superimposed esterification coproduction of carbon four isooctene, sec-butyl acetate after ether as claimed in claim 1, is characterized in that: the iso-butylene content≤2.5wt% after described ether in carbon four raw materials, 1.5 times of methanol content≤iso-butylene content.
3. the method for the superimposed esterification coproduction of carbon four isooctene, sec-butyl acetate after ether as claimed in claim 1, is characterized in that: described solid acid catalyst comprises at least one in strong acidic ion resin, molecular sieve, heteropolyacid catalyst.
4. the method for the superimposed esterification coproduction of carbon four isooctene, sec-butyl acetate after ether as claimed in claim 3, it is characterized in that: described storng-acid cation exchange resin is at pore-creating agent, to exist low suspension copolymerization to obtain polystyrene resin by styrene-divinylbenzene, and then with the vitriol oil, oleum or sulphur trioxide, carry out that sulfonation obtains; Described molecular sieve comprises Y-series, ZSM series, MCM series or β Series Molecules sieve; Described heteropolyacid catalyst comprises the heteropolyacid of Keggin structure, Dawson structure, Anderson structure or Silverton structure.
5. the method for the superimposed esterification coproduction of carbon four isooctene, sec-butyl acetate after ether as claimed in claim 4, is characterized in that: described heteropolyacid catalyst is the mixture of wolframic acid and molybdic acid and the mixture of their hydrate.
6. the method for the superimposed esterification coproduction of carbon four isooctene, sec-butyl acetate after ether as claimed in claim 1, is characterized in that: in described esterification, the molar ratio of acetic acid and refining carbon four is 2～4.
7. the method for the superimposed esterification coproduction of carbon four isooctene, sec-butyl acetate after ether as claimed in claim 1, is characterized in that: the charging air speed of described building-up reactions is 0.2～20h
-1, the charging air speed of described esterification is 0.5-3h
-1.
8. the method for the superimposed esterification coproduction of carbon four isooctene, sec-butyl acetate after ether as claimed in claim 7, is characterized in that: the charging air speed of described building-up reactions is 0.5～1.2h
-1, the charging air speed of described esterification is 0.5-1h
-1.
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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 |
| CN103657720B (en) * | 2013-12-10 | 2015-07-01 | 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 |
| 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 |
| CN112341303B (en) * | 2019-08-07 | 2023-01-17 | 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 |
| 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 |
| 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 |
| 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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| CN1037263C (en) * | 1992-12-03 | 1998-02-04 | 中国石油化工总公司石家庄炼油厂 | Preparation method and equipment of diisobutene or triisobutene |
| CN1085652C (en) * | 1997-12-03 | 2002-05-29 | 中国石油化工集团公司 | Method for preparing organic acidic ester |
| CN1172888C (en) * | 2000-12-06 | 2004-10-27 | 中国科学院大连化学物理研究所 | Process for preparing diisobutylene |
| CN1211458C (en) * | 2001-04-18 | 2005-07-20 | 中国石油化工股份有限公司 | Process for preparing isooctane and liquefied petroleum gas for vehicle by oligomerizing and hydrogenating mixed C4 |
| CN101402540B (en) * | 2008-07-16 | 2012-10-31 | 岳阳桦科化工有限责任公司 | Method for producing isooctene with coproduction of sec-butyl carboxylate with selective superposition of butylene |
| CN101402566B (en) * | 2008-07-16 | 2013-01-09 | 岳阳桦科化工有限责任公司 | Method for producing high-purity low-class fatty acid ester |
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