CN103772113B - A kind of method of methyl tertiary butyl ether cracking isobutene polymer grade - Google Patents
A kind of method of methyl tertiary butyl ether cracking isobutene polymer grade Download PDFInfo
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Abstract
The invention discloses a kind of method of methyl tertiary butyl ether cracking isobutene polymer grade.The method comprises: methyl tertiary butyl ether obtains split product through cracking, this split product is after water wash column process, obtain the thick product of iso-butylene, the thick product of wherein said iso-butylene obtains isobutene polymer grade product after the fractionation by adsorption of adsorption tower, and the sorbent material wherein loaded in adsorption tower is LTA molecular sieve, amorphous aluminum silicide and FAU molecular sieve.The inventive method can remove dme, methyl alcohol, water and polyisobutene etc. in the thick product of iso-butylene effectively, and reduces investment and energy consumption, makes device obtain isobutene polymer grade product on more maneuverable basis.
Description
Technical field
The present invention relates to a kind of method for methyl tertiary butyl ether (MTBE) cracking isobutene polymer grade product.
Background technology
Iso-butylene is important Organic Chemicals.With iso-butylene be main raw material produce derived product time, because of product difference the purity requirement of iso-butylene is also not quite similar, particularly to the production of isobutene polymer grade, require higher.
The production of isobutene polymer grade is the needs in order to satisfied synthesis isoprene-isobutylene rubber greatly.In recent years, along with the consumption of butyl rubber inner tube, radial tyre, Medical bottle stopper, water-proof material increases, the consumption of isoprene-isobutylene rubber is constantly increased, especially China.According to " 2010-2015 China synthetic rubber trade investment is analyzed and Potential Prediction report " display that middle throwing consultant issues, the Apparent con-sumption of Chinese isoprene-isobutylene rubber in 1998 only has 2.5 ten thousand tons, calendar year 2001, isoprene-isobutylene rubber Apparent con-sumption also only had 4.6 ten thousand tons, within 2002, be increased to 6.7 ten thousand tons, within 2003, be increased to 100,000 tons further, within 2006, be increased to 20.65 ten thousand tons, within 2009, reach 25.82 ten thousand tons.Expect 2014, the aggregate demand of Chinese isoprene-isobutylene rubber will reach 350,000 tons.And higher to the requirement of iso-butylene raw material (polymerization-grade) when synthesizing isoprene-isobutylene rubber, in table 1.
Table 1 synthesizes the specification of the isobutene polymer grade of isoprene-isobutylene rubber
| Isobutene polymer grade | Content |
| Iso-butylene, wt% | ≥99.7 |
| Methyl tertiary butyl ether (MTBE), μ g/g | ≤10 |
| Methyl alcohol (CH3OH), μ g/g | ≤50 |
| Dme (DME), μ g/g | ≤50 |
| The trimethyl carbinol (TBA), μ g/g | ≤10 |
| Butene-1, μ g/g | ≤100 |
| Butene-2, μ g/g | ≤100 |
| Divinyl, μ g/g | ≤50 |
| Water, μ g/g | ≤50 |
| Dipolymer (DIB), μ g/g | ≤50 |
MTBE cracking is many a kind of methods preparing advanced technology in high-purity isobutylene method, better economy.In MTBE cracking high-purity isobutylene reaction process, main reaction is under the effect of catalyzer, and methyl tertiary butyl ether is cracked into iso-butylene and methyl alcohol, and it is Diisobutylene that side reaction is mainly 1. isobutene polymerisation; 2. methanol dehydration generates dme.US6072095 is that a kind of liquid phase method prepares the method for high-purity iso-butylene by ether-splitting solution, 160 DEG C, under the reaction conditions of 0.7MPa, MTBE transformation efficiency about 90%, containing the dme of 0.5% and the Diisobutylene of 1.1% in reaction product.CN1161881A discloses a kind of modified silica-gel catalyst for methyl tertiary butyl ether cracking iso-butylene.This catalyzer is in temperature of reaction 180 ~ 220 DEG C, reaction pressure 0.1 ~ 0.8MPa, weight space velocity 2 ~ 6h
-1condition under the transformation efficiency of methyl tertiary butyl ether and the selectivity of iso-butylene can reach 100%, the amount of the by product dme simultaneously generated accounts for 0.3%.CN02146148.1 discloses a kind of method of producing iso-butylene combined producing dimethyl ether and Diisobutylene, and its object product is dme and iso-butylene.
All in all, for MTBE cracking for isobutene polymer grade, being separated (process) after iso-butylene is very important link.The post-treating method generally adopted at present is rectifying separation, and namely split product is from reactor bottom extraction, enters water wash column through heat exchange.In product after water wash column process most methyl alcohol, water, unreacted completely MTBE, dme etc. bottom flow out enter into method separation tower and methanol rectifying tower.Dipolymer still containing a small amount of methyl alcohol, water, dme and iso-butylene in the iso-butylene of top extraction or trimer.In order to improve iso-butylene purity further, must through iso-butylene weight-removing column (taking off the relevant heavy constituents such as diisobutylene), iso-butylene lightness-removing column (the de-relevant light constituent such as dme, azeotropic water) just the high-purity iso-butylene of finished product can be obtained after refining.The factor such as stage number, operational condition of the purity of high-purity iso-butylene and water wash column, iso-butylene weight-removing column and iso-butylene lightness-removing column is closely bound up.Typical high-purity iso-butylene Production Flow Chart adopts " anti-six towers " (i.e. reactor, MTBE treating tower, water wash column, methanol distillation column, refining methanol tower, iso-butylene weight-removing column, an iso-butylene lightness-removing column), as Fig. 1.
Although MTBE cracking is for the rear distillation technology comparative maturity of iso-butylene technology, there are the problems such as tower number is more, investment is large, operational condition is wayward, energy consumption is higher, product cost is high.For this reason, CN101024595A by original be used for iso-butylene after two iso-butylene treating towers being separated all cancel (also eliminating refining methanol tower) simultaneously, typical preparation flow is changed into " anti-three towers ", make operation comparatively easy, device total energy consumption have dropped 32.32%, but isolated iso-butylene product purity do not reach the requirement of polymerization-grade raw material.CN101260016A discloses a kind of refining plant and processing method of preparing high-pure isobutene by cracking methyl tertiary butyl ether, in the method, the rear separation of iso-butylene is except the iso-butylene weight-removing column that retains traditional technology and iso-butylene lightness-removing column, turn increase a water wash column system, be equivalent to " anti-seven towers " technical process, the production of purity at 99.7% isobutene polymer grade can be met, and make refrigeration cycle water zero discharge.But the water wash column that the method increases makes investment and process cost raise, must adopt many rounds distribution internals, the control of operational condition is more difficult.
Summary of the invention
For weak point of the prior art, the invention provides a kind of method of methyl tertiary butyl ether cracking isobutene polymer grade.The inventive method can remove dme, methyl alcohol, water and polyisobutene etc. in the thick product of iso-butylene effectively, and reduces investment and energy consumption, makes device obtain isobutene polymer grade product on more maneuverable basis.
The method of methyl tertiary butyl ether cracking isobutene polymer grade of the present invention, comprise: methyl tertiary butyl ether obtains split product through cracking, this split product is after water wash column process, obtain the thick product of iso-butylene, the thick product of iso-butylene obtains isobutene polymer grade product after the fractionation by adsorption of adsorption tower, and the sorbent material wherein loaded in adsorption tower is LTA molecular sieve, amorphous aluminum silicide and FAU molecular sieve.
In the inventive method, the best packing sequence of sorbent material used in adsorption tower is: load LTA molecular sieve, amorphous aluminum silicide and FAU molecular sieve successively along stream flow direction.
In the inventive method, adsorbent amount used in adsorption tower: with the cumulative volume of sorbent material for benchmark, LTA molecular sieve accounts for 10v% ~ 40v%, and amorphous aluminum silicide accounts for 20v% ~ 50v%, and surplus is FAU molecular sieve.
In the inventive method, methyl tertiary butyl ether obtains split product through cracking, and this split product, after water wash column process, obtains the thick product of iso-butylene.This process is the part adopting common process, such as Fig. 1.The catalyzer that methyl tertiary butyl ether cracking adopts is generally silica gel, Zeo-karb, loading type inorganic acid salt, solid phosphoric acid catalyst or acidic molecular sieve etc., and operational condition is generally temperature 220 DEG C ~ 400 DEG C, air speed 1.0h
-1~ 4.0h
-1, pressure 0.1MPa ~ 0.2MPa.
In the inventive method, the thick product of the iso-butylene obtained after water wash column process, based on iso-butylene, also containing the impurity such as dme, methyl alcohol, water and polyisobutene, wherein preferably dme content is not more than 1.5wt%, the content of methyl alcohol is not more than 1.0wt%, the content of water is not more than 1.5wt%.
In the inventive method, the operational condition of described adsorption tower is as follows: adsorption temp is room temperature ~ 90 DEG C, and be preferably 60 DEG C ~ 80 DEG C, adsorptive pressure is 0.1MPa ~ 2.5MPa, and be preferably 0.1MPa ~ 0.2MPa, feed volume air speed is 200h
-1~ 2000h
-1, be preferably 400h
-1~ 1200h
-1.
The shape of described sorbent material is without particular limitation, spherical, particulate state etc. can be selected according to condition, can adopt traditional agglomeration technique, such as rotary table granulation, the size of particle controls by regulating the obliquity of rotating disk, the rotating disk degree of depth, velocity of rotation and consumption of binder.The particle diameter of sorbent material is generally 0.5mm ~ 8.0mm.
Described sorbent material, LTA molecular sieve is one or both in 5A molecular sieve and 4A molecular sieve.The character of LTA molecular sieve is as follows: specific surface area 540m
2/ g ~ 750m
2/ g, preferred 580m
2/ g ~ 700m
2/ g; Pore volume 0.25mL/g ~ 0.31mL/g, preferred 0.27mL/g ~ 0.30mL/g.LTA molecular sieve can adopt ordinary method to synthesize, such as hydrothermal method.Described LTA molecular sieve can adopt former powder, also can adopt through modification LTA molecular sieve, preferably adopt the LTA molecular sieve of one or more modifications in the properties-correcting agent such as calcium, lithium, iron, wherein properties-correcting agent in the content of element in LTA molecular sieve for 0.5wt% ~ 2.0wt%.
In described amorphous aluminum silicide, SiO
2weight content be 10% ~ 75%, average pore diameter is 1.0nm ~ 6.0nm, preferred 2.0nm ~ 4.0nm; Specific surface area 350m
2/ g ~ 650m
2/ g, preferred 400m
2/ g ~ 600m
2/ g; Pore volume 0.50mL/g ~ 1.20mL/g, preferred 0.6mL/g ~ 1.00mL/g.Amorphous aluminum silicide can adopt the method synthesis such as GB2166971, CN1597093A or adopt other synthetic methods.
Described FAU molecular sieve is one or both in X-type molecular sieve and Y zeolite.The SiO of described FAU molecular sieve
2/ Al
2o
3mol ratio is 2.0 ~ 30.0, specific surface area 600m
2/ g ~ 950m
2/ g, preferred 630m
2/ g ~ 900m
2/ g; Pore volume 0.30mL/g ~ 0.38mL/g, preferred 0.32mL/g ~ 0.36mL/g.FAU molecular sieve can adopt ordinary method to synthesize, such as USP4, and 166, the directing agent method synthesis described by 099, also can adopt additive method to synthesize.Described FAU molecular sieve can adopt former powder, also can adopt through modification FAU molecular sieve, preferably adopts through acid-treated FAU molecular sieve.Described FAU molecular sieve further preferred character is as follows: the pore volume of bore dia shared by the duct of 6nm ~ 9nm accounts for 5% ~ 30% of total pore volume.The described preparation process through acid-treated FAU molecular sieve is as follows: FAU molecular sieve is placed in the acid solution that concentration is 0.5mol/L ~ 5.0mol/L, as one or more in nitric acid, hydrochloric acid, oxalic acid etc., at 30 DEG C ~ 90 DEG C temperature, process 4h ~ 24h, be preferably 8h ~ 16h, then dry.The present invention preferably adopts through acid-treated FAU molecular sieve, makes the mesopore orbit generating a large amount of non-FAU type framework of molecular sieve in FAU molecular sieve, effectively increases FAU type molecular sieve adsorption ability and loading capacity.
Need to regenerate after described adsorbent reaches capacity, the operational condition of regeneration is as follows: regeneration pressure is 0.1MPa ~ 0.3MPa, regeneration temperature is 80 DEG C ~ 220 DEG C, one or more in employing nitrogen, helium, stack gas, methane, butane are as regenerating medium, adsorbed adsorptive is removed from sorbent material, recovers the absorption property of sorbent material and recycle.
Containing dme, first alcohol and water etc. in thick iso-butylene material, remove from iso-butylene lightness-removing column and weight-removing column in the traditional technology of MTBE cracking iso-butylene.Cancel iso-butylene lightness-removing column and weight-removing column in the present invention, but adopt adsorption tower, wherein the selection of sorbent material is a very important problem.For the adsorbing and removing of dme, methyl alcohol, water and polyisobutene, certain single adsorption agent can be adopted to produce high-purity iso-butylene, but the index request that will meet isobutene polymer grade still have certain difficulty.The present invention adopts three kinds of sorbent material grading loadings, more effectively except anhydrating, methyl alcohol, dme and polyisobutene, the utilization ratio of sorbent material is high, and remove percentage of admixture high, the purity of gained iso-butylene is high.In addition, the inventive method is flexible to operation, energy-efficient.
Accompanying drawing explanation
Fig. 1 typically prepares high-purity iso-butylene schematic flow sheet; Wherein 1, MTBE treating tower, 2, cracking reactor, 3, water wash column, 4, methanol distillation column, 5, refining methanol tower, 6, iso-butylene weight-removing column, 7, iso-butylene lightness-removing column.
The high-purity iso-butylene schematic flow sheet of Fig. 2 preparation of the present invention; Wherein 1, MTBE treating tower, 2, cracking reactor, 3, water wash column, 4, methanol distillation column, 5, refining methanol tower, 8, adsorption tower.
Embodiment
In the inventive method, wt% is massfraction, and v% is volume fraction.
Composition graphs 1 and Fig. 2 are described as follows the inventive method:
Fig. 1 is the high-purity iso-butylene schematic flow sheet of typical preparation.MTBE first through MTBE treating tower 1 carry out refining after, enter cracking reactor 2 and carry out scission reaction under the operational condition be suitable for, split product enters water wash column 3, the bottoms of water wash column enters methanol distillation column 4 successively and refining methanol tower 5 reclaims methyl alcohol, the thick product of water wash column overhead materials iso-butylene enters iso-butylene weight-removing column 6 and iso-butylene lightness-removing column 7 successively, finally obtains object product.
Fig. 2 is the high-purity iso-butylene schematic flow sheet of preparation of the present invention.MTBE first through MTBE treating tower 1 carry out refining after, enter cracking reactor 2 and carry out scission reaction under the operational condition be suitable for, split product enters water wash column 3, the bottoms of water wash column enters methanol distillation column 4 successively and refining methanol tower 5 reclaims methyl alcohol, the thick product introduction adsorption tower 8 of water wash column overhead materials iso-butylene carries out fractionation by adsorption except anhydrating, methyl alcohol, dme and polyisobutene etc., obtains high-purity iso-butylene.
The embodiment of the present invention and the comparative example thick product of iso-butylene used adopt methyl tertiary butyl ether to obtain split product through cracking, the catalyzer that this cracking uses is Ni (0.2wt%)/amorphous silicon Al catalysts, temperature of reaction 220 DEG C, reaction pressure 0.1MPa, MTBE liquid volume air speed is 4h
-1reaction conditions under to be obtained by reacting.Gained split product obtains the thick product of iso-butylene after water wash column process, and its composition is in table 2.
The composition of the thick product of table 2 iso-butylene
| Material | Iso-butylene | Dme | Methyl alcohol | Water | Diisobutylene and triisobutene |
| Content, wt% | 97.21 | 1.05 | 0.85 | 0.35 | 0.54 |
Comparative example 1
Employing is of a size of in Φ 100mm() adsorption tower of × 1100mm, interior filling 13X adsorbent of molecular sieve, its main character is as follows: specific surface area 647m
2/ g, total pore volume 0.35mL/g, SiO
2/ Al
2o
3mol ratio is 2.6, and particle diameter is 1.5mm, and tap density is 0.62g/mL.Adsorption tower temperature is raised to 80 DEG C, and by volume air speed is 500h
-1metering passes into the thick product of iso-butylene preserved through 80 DEG C of constant temperature from top to bottom under 0.1MPa.Every 4h sampling analysis.The results are shown in Table 3.
Comparative example 2
Employing is of a size of in Φ 100mm() adsorption tower of × 1100mm, interior filling Y zeolite sorbent material, its main character is as follows: specific surface area 871m
2/ g, total pore volume 0.36mL/g, SiO
2/ Al
2o
3mol ratio is 9.1, and particle diameter is 1.5mm, and the pore volume of bore dia shared by the duct of 6nm ~ 9nm accounts for 20% of total pore volume.Adsorption tower temperature is raised to 80 DEG C, and by volume air speed is 500h
-1metering passes into the thick product of iso-butylene preserved through 80 DEG C of constant temperature from top to bottom under 0.1MPa.Every 4h sampling analysis.The results are shown in Table 3.The preparation method of Y molecular sieve sorbent material is as follows: NaY molecular sieve is placed in the nitric acid acid solution that concentration is 1.0mol/L, at 50 DEG C of temperature, processes 12h, then dry and obtain.
Comparative example 3
Employing is of a size of in Φ 100mm() adsorption tower of × 1100mm, interior filling amorphous aluminum silicide sorbent material.Its main character is as follows: specific surface area 379m
2/ g, total pore volume 0.61mL/g, SiO
2/ Al
2o
3mol ratio is 2.2, and particle diameter is 1.5mm, and tap density is 0.58g/mL.Adsorption tower temperature is raised to 80 DEG C, and by volume air speed is 500h
-1metering passes into the thick product of iso-butylene preserved through 80 DEG C of constant temperature from top to bottom under 0.1MPa.Every 4h sampling analysis.The results are shown in Table 3.
Comparative example 4
Employing is of a size of in Φ 100mm() adsorption tower of × 1100mm, interior filling 4A adsorbent of molecular sieve, its main character is as follows: specific surface area 712m
2/ g, total pore volume 0.29mL/g, SiO
2/ Al
2o
3mol ratio is 2, and particle diameter is 3.0mm, and tap density is 0.68g/mL.Adsorption tower temperature is raised to 80 DEG C, and by volume air speed is 1200h
-1metering at 0.2 mpa metering from top to bottom passes into the thick product of iso-butylene preserved through 80 DEG C of constant temperature.Every 4h sampling analysis.The results are shown in Table 3.
Comparative example 5
Employing is of a size of in Φ 100mm() adsorption tower of × 1100mm, the 5A adsorbent of molecular sieve of interior filling iron modification.Method of modifying is as follows: the iron nitrate solution being 1.0mol/L by 5A molecular sieve and concentration mixes, and the pH regulating mixing solutions with nitric acid is 7, at 60 DEG C, react 12h, again through cooling, washing, filtration, and in 100 DEG C of dry 4h, obtain iron modification 5A zeolite molecular sieve, wherein iron level is 1.2w%.Its main character is as follows: specific surface area 625m
2/ g, total pore volume 0.29mL/g, SiO
2/ Al
2o
3mol ratio is 2, and particle diameter is 1.5mm, and tap density is 0.68g/mL.Adsorption tower temperature is raised to 80 DEG C, and by volume air speed is 500h
-1metering passes into the thick product of iso-butylene preserved through 80 DEG C of constant temperature from top to bottom under 0.1MPa.Every 4h sampling analysis.The results are shown in Table 3.
Table 3 is by the composition of iso-butylene after adsorption tower
| Composition | Iso-butylene, wt% | Dme, μ g/g | Methyl alcohol, μ g/g | Water, μ g/g | Diisobutylene and triisobutene, μ g/g |
| Comparative example 1 | |||||
| 4h | 99.88 | 96 | 989 | 91 | 36 |
| 8h | 99.87 | 87 | 1100 | 102 | 45 |
| 12h | 99.85 | 192 | 1059 | 195 | 46 |
| 16h | 99.76 | 305 | 1725 | 287 | 70 |
| 20h | 99.74 | 410 | 1777 | 312 | 75 |
| 24h | 99.64 | 595 | 2390 | 565 | 75 |
| Comparative example 2 | |||||
| 4h | 99.87 | 105 | 1028 | 85 | 56 |
| 8h | 99.86 | 134 | 1124 | 90 | 62 |
| 12h | 99.83 | 185 | 1243 | 169 | 62 |
| 16h | 99.78 | 296 | 1517 | 258 | 78 |
| 20h | 99.76 | 365 | 1645 | 293 | 80 |
| 24h | 99.68 | 605 | 2060 | 433 | 85 |
| Comparative example 3 | |||||
| 4h | 99.80 | 1221 | 50 | 586 | 135 |
| 8h | 99.80 | 1250 | 48 | 527 | 130 |
| 12h | 99.74 | 1460 | 151 | 567 | 165 |
| 16h | 99.70 | 1686 | 239 | 856 | 170 |
| 20h | 99.60 | 2523 | 266 | 1021 | 200 |
| 24h | 99.57 | 2617 | 374 | 1101 | 213 |
| Comparative example 4 | |||||
| 4h | 99.70 | 2279 | 167 | 35 | 456 |
| 8h | 99.66 | 2624 | 236 | 40 | 512 |
| 12h | 99.56 | 3016 | 329 | 65 | 960 |
| 16h | 99.53 | 3091 | 451 | 103 | 1014 |
| 20h | 99.47 | 3345 | 456 | 131 | 1356 |
| 24h | 99.43 | 3416 | 521 | 167 | 1622 |
| Comparative example 5 | |||||
| 4h | 99.74 | 2053 | 144 | 19 | 367 |
| 8h | 99.65 | 2711 | 256 | 25 | 516 |
| 12h | 99.58 | 2906 | 349 | 44 | 950 |
| 16h | 99.55 | 2936 | 475 | 126 | 998 |
| 20h | 99.47 | 3342 | 485 | 154 | 1342 |
| 24h | 99.36 | 4054 | 580 | 234 | 1569 |
As can be seen from Table 3, although adopt single sorbent material to have good adsorptive power, loading capacity is still not enough with the ability removing dme, methyl alcohol, water and polyisobutene, and the utilization ratio of sorbent material is lower.
Embodiment 1
Employing is of a size of in Φ 100mm() adsorption tower of × 1100mm, load 13X molecular sieve, amorphous aluminum silicide and each 1/3(of 5A adsorbent of molecular sieve that the comparative example 1 of 1.5mm size, comparative example 3 and comparative example 5 use from bottom to top successively by volume).Adsorption tower temperature is raised to 80 DEG C, and by volume air speed is 500h
-1metering passes into the thick product of iso-butylene preserved through 80 DEG C of constant temperature from top to bottom under 0.1MPa.Every 4h sampling analysis.The results are shown in Table 4.
Embodiment 2
Employing is of a size of in Φ 100mm() adsorption tower of × 1100mm, by volume 10:20:70 load successively from bottom to top 1.5mm size as comparative example 1, comparative example 3 and comparative example 5 the 13X molecular sieve, amorphous aluminum silicide and the 5A molecular sieve that use.Adsorption tower temperature is raised to 80 DEG C, and by volume air speed is 500h
-1metering passes into the thick product of iso-butylene preserved through 80 DEG C of constant temperature from top to bottom under 0.1MPa.Every 4h sampling analysis.The results are shown in Table 4.
Embodiment 3
Employing is of a size of in Φ 100mm() adsorption tower of × 1100mm, by volume 20:50:30 load successively from bottom to top 3.0mm size as comparative example 2, comparative example 3 and comparative example 4 use by Y zeolite, amorphous aluminum silicide and 4A adsorbent of molecular sieve.Adsorption tower temperature is raised to 80 DEG C, and by volume air speed is 1200h
-1metering passes into the thick product of iso-butylene preserved through 80 DEG C of constant temperature at 0.2 mpa from top to bottom.Every 4h sampling analysis.The results are shown in Table 4.
Table 4 is by the composition of iso-butylene after grating adsorption tower
| Composition | Iso-butylene, wt% | Dme, μ g/g | Methyl alcohol, μ g/g | Water, μ g/g | Diisobutylene and triisobutene, μ g/g |
| Embodiment 1 | |||||
| 4h | 99.97 | 115 | 77 | 64 | 58 |
| 8h | 99.96 | 145 | 89 | 67 | 55 |
| 12h | 99.95 | 170 | 135 | 80 | 82 |
| 16h | 99.94 | 173 | 195 | 81 | 112 |
| 20h | 99.91 | 315 | 234 | 109 | 267 |
| 24h | 99.90 | 320 | 218 | 135 | 294 |
| Embodiment 2 | |||||
| 4h | 99.99 | 34 | 42 | 28 | 35 |
| 8h | 99.98 | 62 | 75 | 45 | 42 |
| 12h | 99.98 | 65 | 70 | 53 | 49 |
| 16h | 99.97 | 68 | 105 | 75 | 52 |
| 20h | 99.95 | 125 | 169 | 135 | 81 |
| 24h | 99.93 | 196 | 224 | 150 | 128 |
| Embodiment 3 | |||||
| 4h | 99.96 | 175 | 75 | 55 | 69 |
| 8h | 99.95 | 199 | 126 | 78 | 72 |
| 12h | 99.94 | 235 | 131 | 102 | 113 |
| 16h | 99.92 | 325 | 145 | 165 | 145 |
| 20h | 99.90 | 430 | 175 | 186 | 196 |
| 24h | 99.89 | 480 | 178 | 196 | 225 |
As can be seen from Table 4, adopt the thick product of grating purification iso-butylene that LTA molecular sieve, amorphous aluminum silicide and FAU molecular sieve are suitable, loading capacity is high, and the utilization ratio of sorbent material is high, removes dme, methyl alcohol, water and polyisobutene efficiency high.
Claims (15)
1. the method for a methyl tertiary butyl ether cracking isobutene polymer grade, comprise: methyl tertiary butyl ether obtains split product through cracking, this split product is after water wash column process, obtain the thick product of iso-butylene, it is characterized in that the thick product of described iso-butylene obtains isobutene polymer grade product after the fractionation by adsorption of adsorption tower, the sorbent material wherein loaded in adsorption tower is LTA molecular sieve, amorphous aluminum silicide and FAU molecular sieve; The packing sequence of sorbent material used in described adsorption tower is: load LTA molecular sieve, amorphous aluminum silicide and FAU molecular sieve successively along stream flow direction; Adsorbent amount used in described adsorption tower: with the cumulative volume of sorbent material for benchmark, LTA molecular sieve accounts for 10v% ~ 40v%, and amorphous aluminum silicide accounts for 20v% ~ 50v%, and surplus is FAU molecular sieve; Adsorption temp is 60 ~ 80 DEG C, and adsorptive pressure is 0.1 ~ 0.2MPa, and feed volume air speed is 400 ~ 1200h
-1.
2. in accordance with the method for claim 1, it is characterized in that the thick product of described iso-butylene, based on iso-butylene, containing dme, methyl alcohol, water and polyisobutene.
3. in accordance with the method for claim 2, it is characterized in that in the thick product of described iso-butylene, the content of dme is not more than 1.5wt%, the content of methyl alcohol is not more than 1.0wt%, the content of water is not more than 1.5wt%.
4. in accordance with the method for claim 1, it is characterized in that the shape of described sorbent material selects spherical or particulate state, the particle diameter of sorbent material is 0.5mm ~ 8.0mm.
5. in accordance with the method for claim 1, it is characterized in that described LTA molecular sieve is one or both in 5A molecular sieve and 4A molecular sieve.
6. in accordance with the method for claim 1, it is characterized in that described LTA molecular sieve is the LTA molecular sieve of one or more modifications in properties-correcting agent calcium, lithium, iron, wherein properties-correcting agent in the content of element in LTA molecular sieve for 0.5wt% ~ 2.0wt%.
7., according to the method described in claim 1,5 or 6, it is characterized in that the specific surface area 540m of described LTA molecular sieve
2/ g ~ 750m
2/ g, pore volume 0.25mL/g ~ 0.31mL/g.
8. in accordance with the method for claim 1, it is characterized in that in described amorphous aluminum silicide, SiO
2weight content be 10% ~ 75%, average pore diameter is 1.0nm ~ 6.0nm, specific surface area 350m
2/ g ~ 650m
2/ g, pore volume 0.50mL/g ~ 1.20mL/g.
9. in accordance with the method for claim 1, it is characterized in that in described amorphous aluminum silicide, SiO
2weight content be 10% ~ 75%, average pore diameter is 2.0nm ~ 4.0nm, and specific surface area is 400m
2/ g ~ 600m
2/ g, pore volume is 0.6mL/g ~ 1.00mL/g
10. in accordance with the method for claim 1, it is characterized in that described FAU molecular sieve is one or both in X-type molecular sieve and Y zeolite.
11. in accordance with the method for claim 1, it is characterized in that the SiO of described FAU molecular sieve
2/ Al
2o
3mol ratio is 2.0 ~ 30.0, specific surface area 600m
2/ g ~ 950m
2/ g, pore volume 0.30mL/g ~ 0.38mL/g.
12. in accordance with the method for claim 1, it is characterized in that described FAU molecular sieve is through acid-treated FAU molecular sieve.
13. according to the method described in claim 1 or 11, it is characterized in that in described FAU molecular sieve, and the pore volume of bore dia shared by the duct of 6nm ~ 9nm accounts for 5% ~ 30% of total pore volume.
14. in accordance with the method for claim 12, it is characterized in that: FAU molecular sieve is as follows through acid-treated process: FAU molecular sieve is placed in the acid solution that concentration is 0.5mol/L ~ 5.0mol/L, wherein acid adopts one or more in nitric acid, hydrochloric acid, oxalic acid, 4h ~ 24h is processed at 30 DEG C ~ 90 DEG C temperature, then dry.
15. in accordance with the method for claim 1, it is characterized in that described adsorbent needs to regenerate after reaching capacity, the operational condition of regeneration is as follows: regeneration pressure is 0.1MPa ~ 0.3MPa, regeneration temperature is 80 DEG C ~ 220 DEG C, and one or more in employing nitrogen, helium, stack gas, methane, butane are as regenerating medium.
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| EP0100604A1 (en) * | 1982-07-02 | 1984-02-15 | Summit Gas Systems Pte. Ltd. | Process for converting methanol and/or dimethyl ether to iso-c4 compounds, and catalysts for use therein |
| CN86108873A (en) * | 1985-12-16 | 1987-08-19 | 联合碳化公司 | Recovery of dimethyl ether from liquid phase C3-C5 olefin feedstocks |
| CN1569612A (en) * | 2004-04-29 | 2005-01-26 | 中国科学院山西煤炭化学研究所 | Method for purifying synthesis gas from methanol cracking |
| CN101260016A (en) * | 2008-04-23 | 2008-09-10 | 天津大学 | Refining device for preparing high-pure isobutene by cracking methyl tertiary butyl ether and technique thereof |
| CN101703869A (en) * | 2009-10-28 | 2010-05-12 | 马军 | New method and device for recovering organic solvent from waste gas |
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| EP0100604A1 (en) * | 1982-07-02 | 1984-02-15 | Summit Gas Systems Pte. Ltd. | Process for converting methanol and/or dimethyl ether to iso-c4 compounds, and catalysts for use therein |
| CN86108873A (en) * | 1985-12-16 | 1987-08-19 | 联合碳化公司 | Recovery of dimethyl ether from liquid phase C3-C5 olefin feedstocks |
| CN1569612A (en) * | 2004-04-29 | 2005-01-26 | 中国科学院山西煤炭化学研究所 | Method for purifying synthesis gas from methanol cracking |
| CN101260016A (en) * | 2008-04-23 | 2008-09-10 | 天津大学 | Refining device for preparing high-pure isobutene by cracking methyl tertiary butyl ether and technique thereof |
| CN101703869A (en) * | 2009-10-28 | 2010-05-12 | 马军 | New method and device for recovering organic solvent from waste gas |
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