CN106552668A - A kind of method of modifying of cation exchange resin catalyst and its application - Google Patents
A kind of method of modifying of cation exchange resin catalyst and its application Download PDFInfo
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- CN106552668A CN106552668A CN201510624968.6A CN201510624968A CN106552668A CN 106552668 A CN106552668 A CN 106552668A CN 201510624968 A CN201510624968 A CN 201510624968A CN 106552668 A CN106552668 A CN 106552668A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
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Abstract
The invention discloses a kind of method of modifying of cation exchange resin catalyst, including：1) acid compound is dissolved in alcohol organic solvent, the alcoholic solution of acid compound is obtained；2) reacted cation exchange resin catalyst and the alcoholic solution of the acid compound；3) to step 2) product be dried.And after the nature-changed cation resin catalyst of the method acquisition is to the ether method comprehensively utilized by C-4-fraction is disclosed, is comprised the following steps：Step i, after ether, C-4-fraction and acetic acid are reacted in the presence of catalyst, obtain the sec-Butyl Acetate crude product containing acetic acid；There is hydrolysis in step ii, water and the sec-Butyl Acetate crude product containing acetic acid in the presence of the catalyst, the mixture of sec-Butyl Acetate and sec-butyl alcohol is isolated in the mixture obtained from reaction；Step iii, carries out rectifying to the mixture of the sec-Butyl Acetate and sec-butyl alcohol, respectively obtains sec-Butyl Acetate and sec-butyl alcohol product.
Description
Technical field
The present invention relates to petrochemical industry.Further, it is related to a kind of changing for cation exchange resin catalyst
Property method, and the application of the nature-changed cation resin catalyst prepared using the method for modifying.
Background technology
With the C-4-fraction of the change of fossil resources general layout, ethylene plant and oil plant it is more and more valuable, but I
The utilization current to C-4-fraction of state is simultaneously insufficient, using it is most be isobutene and fourth two in C-4-fraction
Alkene.Butadiene is not contained in refinery casing head, etherification reaction, the C-4-fraction of ethylene plant can be directly carried out
In butadiene containing about 45%, need to carry out etherification reaction after Butadiene Extraction again.Methyl- tert fourth is produced at present
The technology of base ether (MTBE) is very ripe, and there is ether-based device in each petroleum chemical enterprise, is evaporated by mixing carbon four
Dividing and methyl tertiary butyl ether(MTBE) being prepared with methyl alcohol reaction, isobutene reacts completely, and after remaining ether, C-4-fraction is alkane
With the mixture of monoolefine (1- butylene, Trans-2-butene and cis-2-butene etc.), wherein monoolefine is valuable change
Work raw material, but be not fully used.
Sec-Butyl Acetate, i.e. sec-butyl acetate, acetic acid dibutyl ester, are one of four kinds of isomers of butyl acetate,
It is for colourless, the inflammable, liquid with fruit taste, in most of the cases all similar to the performance of other isomers,
Dissolvable various kinds of resin and organic matter.Its boiling point is lower than conventional n-butyl acetate and isobutyl acetate, evaporation speed
Degree is very fast.Sec-Butyl Acetate has many uses general, it is adaptable to medicine, coating, high-grade paint, ink, resin and
Acetic acid dehydration and solvent, while MTBE can also be substituted, as the additive of gasoline, be a kind of purposes very
Extensive fine chemicals.In recent years, with butylene and acetic acid as raw material, with strong acidic ion resin as catalysis
The production technology of agent has the advantages that environmental pollution is little, low production cost, causes R＆D institution and manufacturing enterprise
Extensive concern.
Sec-butyl alcohol is the raw material for producing MEK, also serves as solvent.The preparation method of sec-butyl alcohol has indirect hydration
Method and direct hydration method, current commercial plant all adopt direct hydration method.The technique needs the carbon tetraene of high concentration
Hydrocarbon is raw material, and a large amount of C 4 olefins are recycled, and energy consumption is higher.
The catalyst of the production sec-Butyl Acetate disclosed in prior art includes strong acidic ion resin, miscellaneous many
Acid, solid super-strong acid and molecular sieve catalyst.Commercial plant built at present is strong acidic ion resin
Catalyst, but raw material C 4 olefin used needs purification, and lock out operation complexity is loaded down with trivial details, and energy consumption is higher.
In prior art, the preparation method of modified resin catalyst is complicated, and solvent load is big, and resulting changes
Property resin catalyst activity it is also not high, can also produce the swelling (swelling ratio in acetic acid in use at which
﹥ 55%), the phenomenon such as lump, cause bed pressure drop increase, catalytic performance to be deteriorated, until during more catalyst changeout
Dismounting is difficult.
The content of the invention
To overcome defect present in above-mentioned prior art, the invention provides a kind of catalyzing cation exchange resin
The method of modifying of agent, the nature-changed cation resin catalyst activity obtained by the method is high, using
Do not lump in journey, dismounting is easy, good stability, use it for C 4 olefin and acetic acid Zhong Ding is prepared with acetic acid reaction
During ester, C 4 olefin high conversion rate, sec-Butyl Acetate selectivity it is good；Prepare for sec-Butyl Acetate hydrolysis secondary
During butanol, the high conversion rate of sec-Butyl Acetate, sec-butyl alcohol are selectively good, are therefore particularly suitable for carbon four after ether
The comprehensive utilization of cut.
One aspect of the present invention provides a kind of method of modifying of cation exchange resin catalyst, including：
1) acid compound is dissolved in alcohol organic solvent, the alcoholic solution of acid compound is obtained；
2) reacted cation exchange resin catalyst and the alcoholic solution of the acid compound；
3) to step 2) product be dried.
According to the present invention, the cationic ion-exchange resin, preferably macropore strong acid cation exchanger resin, more
Preferably NKC-9, DA-340 or D2006 macroreticular resin.
Cation resin catalyzing agent is modified by the alcoholic solution using acid compound, can strengthen sun from
The acidity of sub- resin catalyst such that it is able to improve the catalytic performance of catalyst, such as catalysis activity, selectivity,
Stability etc.；On the other hand, inventor it has been investigated that, using the aqueous solution of acid compound to cation tree
When fat catalyst is modified, although improve its acid and activity, catalyst has swelling, caking
Phenomenon, and when being modified using the alcoholic solution of acid compound, then can improve the acid, active of catalyst
Selectively simultaneously, the above-mentioned swelling, phenomenon of caking is effectively reduced or avoided, stablizing for catalyst is improve
Property.
The present invention one preferred embodiment in, the acid compound be selected from alchlor, four chlorinations
One or more in tin, sulfamic acid and p-methyl benzenesulfonic acid.
The present invention another preferred embodiment in, the alcohol organic solvent is methyl alcohol, ethanol, just
At least one in propyl alcohol, isopropanol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol, isobutanol and n-amyl alcohol, preferably
For methyl alcohol and/or ethanol.
The present invention another preferred embodiment in, acid chemical combination in the alcoholic solution of the acid compound
The concentration of thing is 0.05-0.15mol/L, preferably 0.08-0.12mol/L.
The present invention another preferred embodiment in, step 2) in, the cationic ion-exchange resin is urged
The w/v of the alcoholic solution of agent and the acid compound is 0.8-1.1:1, preferably 0.9-1:1.
The present invention another preferred embodiment in, step 2) in, reaction temperature be 20-80 DEG C, it is excellent
Elect 25-80 DEG C as, the reaction time is 2-4h.
The present invention another preferred embodiment in, step 3) in, baking temperature be 50-95 DEG C, it is excellent
Elect 70-90 DEG C as, drying time is 2-4h.
Another aspect of the present invention provides a kind of modified cation resin catalyst obtained using above-mentioned method of modifying
The method comprehensively utilized to C-4-fraction after ether, comprises the following steps：
Step i, after ether, C-4-fraction and acetic acid are reacted in the presence of modified cation resin catalyst, are obtained
Sec-Butyl Acetate crude product containing acetic acid；
Step ii, water and the sec-Butyl Acetate crude product containing acetic acid are in modified cation resin catalyst
Effect issues raw hydrolysis, the mixture isolated in the mixture obtained from reaction；
Step iii, carries out rectifying to the mixture of the sec-Butyl Acetate and sec-butyl alcohol, respectively obtains acetic acid Zhong Ding
Ester and sec-butyl alcohol product.
First, using nature-changed cation resin catalyst, C-4-fraction and acetic acid reaction after ether is made, is obtained
Sec-Butyl Acetate crude product containing acetic acid；Without separating-purifying, in nature-changed cation resin catalyst
Under effect, direct hydrolysis can be obtained by the mixture of sec-Butyl Acetate and sec-butyl alcohol；After separating water phase, pass through
Rectifying separates sec-Butyl Acetate and sec-butyl alcohol, can obtain highly purified sec-Butyl Acetate and sec-butyl alcohol product.
Due to modified cation-exchange resin used in the method for the comprehensive utilization of C-4-fraction after above-mentioned ether
Catalyst, promotes the reaction of C 4 olefin and acetic acid, and then improves the conversion ratio of C 4 olefin and improve and vinegar
The selectivity of the secondary butyl ester of acid.Meanwhile, nature-changed cation resin catalyst can further promote acetic acid secondary
Fourth ester hydrolysis, so as to further increase the selectivity of the conversion ratio and sec-butyl alcohol of sec-Butyl Acetate.
According to the present invention, after the ether, C-4-fraction is referred to using in the C-4-fraction of ethylene plant and oil plant
Isobutene synthesizing methyl tertbutyl ether after C-4-fraction.After the ether, C-4-fraction is mainly alkane and monoene
The mixture of hydrocarbon, its main component include iso-butane, normal butane, 1- butylene, Trans-2-butene, cis-2-butene.
According to said method, in step i, with after ether C-4-fraction and acetic acid as raw material, in modified cation
In the presence of exchange resin catalyst, the alkene and acetic acid after ether in C-4-fraction is reacted, and is obtained containing vinegar
The sec-Butyl Acetate crude product of acid, in the process, the alkene almost all after ether in C-4-fraction is anti-with acetic acid
Sec-Butyl Acetate should be generated, in the present invention, the conversion ratio of the alkene after ether in C-4-fraction can reach 99.5%,
And the alkane after ether in C-4-fraction is then not involved in reaction, discharges from reaction system, thus contain vinegar in preparation
While the sec-Butyl Acetate crude product of acid, the separation of alkane and alkene in C-4-fraction after ether is realized.
The present invention one preferred embodiment in, the carbon in step i, after ether in C-4-fraction
Alkatetraenes is 0.70-0.95 with the mol ratio of acetic acid, and the weight space velocity for mixing C-4-fraction is 1-3h-1。
The present invention one preferred embodiment in, in step i, reaction temperature be 70-95 DEG C,
It is preferred that 85-90 DEG C, pressure is 1.0-2.5MPa, preferred 1.5-2MPa.
It is according to said method, in step ii, thick with the sec-Butyl Acetate containing acetic acid obtained in water and step i
Product is raw material, and under the effect effect of nature-changed cation resin catalyst and acetic acid, sec-Butyl Acetate is thick
There is hydrolysis in product, generate acetic acid and sec-butyl alcohol.The yield of sec-butyl alcohol is generated far above by alkene by this process
The aquation of hydrocarbon prepares sec-butyl alcohol.The mixture that reaction is obtained includes acetic acid, sec-butyl alcohol and unreacted water
And sec-Butyl Acetate, water and acetic acid as water phase are first separated, has just obtained secondary as the acetic acid of oil phase
The mixture of butyl ester and sec-butyl alcohol.
The present invention one preferred embodiment in, in step ii, water is slightly produced with sec-Butyl Acetate
The mol ratio of the sec-Butyl Acetate in product is 1.0-1.5, the weight space velocity 1-3h of sec-Butyl Acetate-1。
The present invention one preferred embodiment in, in step ii, reaction temperature be 80-120 DEG C,
Preferably 100-110 DEG C, pressure is 0.6-2.5MPa, preferably 1.5-2MPa.
According to said method, the reaction of step i and ii can be carried out in the reactor, and the reactor is pipe
Formula reactor, tank reactor or tower reactor.
According to said method, in step i, after ether, C-4-fraction and acetic acid are logical from reactor head respectively
Enter reactor；In step ii, water and sec-Butyl Acetate crude product are passed through instead from the top of reactor respectively
Answer device.
According to said method, in the step III, due to boiling point (99.5 DEG C) and the acetic acid Zhong Ding of sec-butyl alcohol
(117.9 DEG C) differences of boiling point of ester are larger, both separation are capable of achieving by common rectifying tower, are respectively obtained
Sec-butyl alcohol and sec-Butyl Acetate product.
The ratio of sec-Butyl Acetate and sec-butyl alcohol product in actual production, can be regulated and controled according to market demand, for example,
When larger to the demand of sec-butyl alcohol product, can be using sec-Butyl Acetate return to step ii for obtaining as reaction raw materials
Recycle；When the demand of the secondary butyl ester of Dichlorodiphenyl Acetate is larger, can be by the sec-Butyl Acetate of part from containing acetic acid
It is directly separated out in sec-Butyl Acetate crude product, does not carry out the reaction of step ii.
According to said method, as the boiling point (119.5 DEG C) of acetic acid differs larger with the boiling point of water, by common
Rectifying column is capable of achieving both separation, respectively obtains water and acetic acid.
The present invention one preferred embodiment in, said method also include step iv, will be isolated
Acetic acid return to step i is recycled as reaction raw materials, former using isolated water return to step ii as reaction
Material is recycled.
The present invention one preferred embodiment in, the acetic acid be purity more than 99.5% glacial acetic acid.
The method of modifying of the cation exchange resin catalyst provided according to the present invention, can be in the acid for improving catalyst
Property and activity while, be effectively reduced or avoided it is above-mentioned it is swelling, caking phenomenon, do not lump in use,
Dismounting easily, good stability, when using it for C 4 olefin and preparing sec-Butyl Acetate with acetic acid reaction, carbon tetraene
Hydrocarbon conversion rate is high, the selectivity of sec-Butyl Acetate is good；When preparing sec-butyl alcohol for sec-Butyl Acetate hydrolysis, acetic acid
The high conversion rate of secondary butyl ester, sec-butyl alcohol are selectively good, are therefore particularly suitable for the comprehensive profit to C-4-fraction after ether
With.
The method of the comprehensive utilization provided according to the present invention, can be with C-4-fraction after the utilization ether of comprehensive high-efficiency, no
The separation of wherein C 4 olefin and butane is realized only, moreover it is possible to obtain highly purified sec-Butyl Acetate and Zhong Ding
Alcohol, and according to actual needs, can flexibly control the ratio of sec-Butyl Acetate and sec-butyl alcohol product.The present invention is carried
For method process is simple, control is flexible, high-efficiency environment friendly, and low production cost is the comprehensive profit of C-4-fraction after ether
One effective way.
Description of the drawings
Process charts of the Fig. 1 for the one embodiment according to the method for providing of the invention.
Description of symbols：A- first reactors, B- second reactors, the first knockout towers of C-, the second knockout towers of D-,
E- first rectifying columns, F- Second distillation columns；C-4-fraction after 1- ethers, 2- acetic acid, the 2 '-acetic acid that recycles,
The mixture that 3- is obtained in first reactor, 4- butanes and the unreacted alkene of very small amount, 5- contain acetic acid
Sec-Butyl Acetate crude product, 6- water, the 6 '-water that recycles, the mixture that 7- is obtained in second reactor,
Oil phases of the 8- in the mixture that second reactor is obtained, water phases of the 9- in the mixture that second reactor is obtained,
10- sec-butyl alcohols, 11- sec-Butyl Acetates.
Specific embodiment
Below in conjunction with the accompanying drawings the specific embodiment of the present invention is described in detail, but be the invention is not restricted to following
Explanation.If no special instructions, the percentage in the present invention is mass percent.
Embodiment 1NKC-9 modified 1#Preparation：
The round bottom that the absolute ethyl alcohol of 2.75 grams of aluminum trichloride (anhydrous)s and 200 milliliters is added separately to 500 milliliters is burnt
In bottle, stirring dissolves aluminum trichloride (anhydrous).By 180 grams of NKC-9 resins and the second dissolved with aluminum trichloride (anhydrous)
Alcoholic solution is added separately in reactor, and reactor is installed (in air-tight state, to prevent solvent from volatilizing),
80 DEG C are heated under agitation, cooling, stopping stirring after 2 hours, temperature of reaction kettle will reaction after being down to room temperature
Kettle is dismantled, and pours out catalyst, is dried 4 hours at 80 DEG C after drying, and taking-up is put into standby in drier.
Embodiment 2NKC-9 modified 2#Preparation：
The methyl alcohol of 2.0 grams of sulfamic acids and 200 milliliters is added separately in 500 milliliters of round-bottomed flask, is stirred
Mixing dissolves sulfamic acid.180 grams of NKC-9 resins and methanol solution dissolved with sulfamic acid are added separately to
In reactor, reactor is installed into (in air-tight state, to prevent solvent from volatilizing), is heated under agitation
80 DEG C, reactor is dismantled after being down to room temperature, pours out and urge by cooling, stopping stirring after 2 hours, temperature of reaction kettle
Agent, dries 4 hours at 80 DEG C after drying, and taking-up is put into standby in drier.
Embodiment 3NKC-9 modified 3#Preparation：
The methyl alcohol of 2.75 grams of p-methyl benzenesulfonic acids and 200 milliliters is added separately to into 500 milliliters of round-bottomed flask
In, stirring dissolves sulfamic acid.By 200 grams of NKC-9 resins and the methanol solution dissolved with p-methyl benzenesulfonic acid
It is added separately in reactor, reactor is installed into (in air-tight state, to prevent solvent from volatilizing), in room
Stir 2 hours under warm (25 DEG C).Stop stirring dismantling reactor, pour out catalyst, 80 after drying
DEG C dry 4 hours, taking-up is put into standby in drier.
Embodiment 4
Reaction raw materials：Acetic acid is glacial acetic acid of the purity more than 99.5%, and after ether, C-4-fraction includes iso-butane
44.19%th, normal butane 13.23%, 1- butylene 14.05%, t-2- butylene 16.55%, isobutene 0.23% and c-2-
Butylene 11.75%, water are deionized water, and catalyst is using NKC-9 modified 1#, in two reactors respectively
Equipped with 50g catalyst.
Step i：After ether, C 4 fraction 1 and acetic acid 2 use measuring pump from the top of first reactor A after pan feeding respectively
Reacted in the presence of catalyst, obtained mixture 3.Reaction condition is：Reaction bed temperature is 85
DEG C, pressure is 1.5MPa, and in C-4-fraction, alkene and acetic acid mol ratio are 0.8, the weight space velocity of C-4-fraction
For 2h-1。
Mixture 3 flows into the first knockout tower C from first reactor bottom and carries out gas-liquid separation, butane and pole
A small amount of unreacted alkene 4 is discharged from the top of the first knockout tower C, the sec-Butyl Acetate crude product 5 containing acetic acid
Flow out from the first knockout tower C bottoms.
Step ii：The sec-Butyl Acetate crude product 5 containing acetic acid flowed out from the first knockout tower C bottoms and water 6
By second reactor B is flowed at the top of measuring pump Jing second reactors, reacted in the presence of catalyst,
Obtain mixture 7.Reaction condition is：Reaction bed temperature is 100 DEG C, and pressure is 1.5MPa, water and vinegar
The secondary butyl ester mol ratio of acid is 1.5, the weight space velocity 1h of sec-Butyl Acetate-1。
Mixture 7 is flowed out from second reactor bottom, into the second knockout tower D, isolated oil phase 8 and water
Phase 9.
Step iii：After oil phase 8 is flowed out from the top of the second knockout tower D, first rectifying column E is flowed into, by essence
Evaporating makes sec-Butyl Acetate separate with sec-butyl alcohol, respectively obtains sec-butyl alcohol 10 and sec-Butyl Acetate 11.
Step iv, after water phase 9 is flowed out from the bottom of the second knockout tower D, flows into Second distillation column F, by essence
Evaporating makes water and acetic acid separated, isolated 2 ' return to step i of acetic acid is recycled, by isolated water
6 ' return to step ii are recycled.
Reaction condition and reaction result are as shown in table 1, table 2 and table 3.
Embodiment 5
Reaction raw materials：Acetic acid be purity more than 99.5% glacial acetic acid, after ether C-4-fraction include iso-butane 0.25%,
Normal butane 20.45%, 1- butylene 5.31%, t-2- butylene 43.72%, isobutene 0.10%, c-2- butylene 30.17%,
Water is deionized water, and catalyst is using modified NKC-9 modified 2#, in two reactors, it is respectively provided with 50g
Catalyst.
The operation of step i, step ii, step iii and step iv is same as Example 1.
Reaction condition and reaction result are as shown in table 1, table 2 and table 3.
Embodiment 6
Reaction raw materials：Acetic acid be purity more than 99.5% glacial acetic acid, after ether C-4-fraction include iso-butane 0.25%,
Normal butane 20.45%, 1- butylene 5.31%, t-2- butylene 43.72%, isobutene 0.10%, c-2- butylene 30.17%,
Water is deionized water, and catalyst is using modified NKC-9 modified 3#, in two reactors, it is respectively provided with 50g
Catalyst.
The operation of step i, step ii, step iii and step iv is same as Example 1.
Reaction condition and reaction result are as shown in table 1, table 2 and table 3.
Comparative example 1
Reaction raw materials：Acetic acid be purity more than 99.5% glacial acetic acid, after ether C-4-fraction include iso-butane 0.25%,
Normal butane 20.45%, 1- butylene 5.31%, t-2- butylene 43.72%, isobutene 0.10%, c-2- butylene 30.17%,
Water is deionized water, and catalyst adopts NKC-9, is respectively provided with 50g catalyst in two reactors.
The operation of step i, step ii, step iii and step iv is same as Example 1.Step i, ii, iii
Reaction condition and reaction result as shown in table 1, table 2, table 3.
The reaction condition and result of 1 step i of table
| Project | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 |
| Catalyst bed depth (DEG C) | 85 | 85 | 85 | 85 |
| Reaction pressure (MPa) | 1.5 | 1.5 | 2.0 | 1.5 |
| C 4 olefin/acetic acid (mol ratio) | 0.8 | 0.8 | 0.8 | 0.8 |
| C 4 fraction weight space velocity (h after ether-1) | 2 | 2 | 2 | 2 |
| Sec-Butyl Acetate is selective (%) | 99.6 | 99.8 | 99.8 | 99.3 |
| C 4 olefin conversion ratio (%) | 90.0 | 99.5 | 97.5 | 84.0 |
The reaction condition and result of 2 step ii of table
| Project | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 |
| Reaction bed temperature (DEG C) | 100 | 100 | 110 | 100 |
| Reaction pressure (MPa) | 2.0 | 1.5 | 1.5 | 1.5 |
| Water/sec-Butyl Acetate (mol ratio) | 1.5 | 1.5 | 1.5 | 1.5 |
| Sec-Butyl Acetate weight space velocity (h-1) | 1 | 1 | 1 | 1 |
| Sec-Butyl Acetate conversion ratio (%) | 80 | 85 | 88 | 74 |
| Sec-butyl alcohol is selective (%) | 95 | 97 | 97 | 90 |
The separating resulting of 3 step iii of table
| Content (%) in oil phase 8 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 |
| Sec-butyl alcohol | 76 | 82 | 85 | 68 |
| Sec-Butyl Acetate | 20 | 15 | 12 | 24 |
According to data in table, the modified cation obtained using the method for modifying provided by the present invention is handed over
Change resin catalyst to comprehensively utilize C-4-fraction after ether, can be evaporated using carbon after ether four in high conversion rate
Point, moreover it is possible to high selectivity obtains sec-Butyl Acetate and sec-butyl alcohol, compares unmodified cationic ion-exchange resin and urges
Agent, the catalysis activity of nature-changed cation resin catalyst and selective being obtained for are obviously improved, especially
It is to significantly improve its conversion ratio to C 4 olefin, reaches more than 90% such that it is able to while playing separation of carbon
The effect of four alkane, is an effective way of C-4-fraction comprehensive utilization after ether.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to the present invention's
Any restriction.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein used
Word is descriptive and explanatory vocabulary, rather than limited vocabulary.Can be by regulation in the claims in the present invention
In the range of the present invention is modified, and the present invention is carried out in without departing substantially from scope and spirit of the present invention
Revision.Although the present invention described in which is related to specific method, material and embodiment, it is not intended that
The present invention is limited to wherein disclosed particular case, conversely, the present invention to can be extended to other all with identical function
Methods and applications.
Claims (10)
1. a kind of method of modifying of cation exchange resin catalyst, including：
1) acid compound is dissolved in alcohol organic solvent, the alcoholic solution of acid compound is obtained；
2) reacted cation exchange resin catalyst and the alcoholic solution of the acid compound；
3) to step 2) product be dried.
2. method of modifying according to claim 1, it is characterised in that the acid compound is selected from trichlorine
Change one or more in aluminium, butter of tin, sulfamic acid and p-methyl benzenesulfonic acid.
3. method of modifying according to claim 1 and 2, it is characterised in that the alcohol organic solvent is
In methyl alcohol, ethanol, normal propyl alcohol, isopropanol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol, isobutanol and n-amyl alcohol
At least one, preferably methyl alcohol and/or ethanol.
4. the method for modifying according to any one of claim 1-3, it is characterised in that the acid chemical combination
In the alcoholic solution of thing, the concentration of acid compound is 0.05-0.15mol/L.
5. the method for modifying according to any one of claim 1-4, it is characterised in that step 2) in,
The w/v of the alcoholic solution of the cation exchange resin catalyst and the acid compound is
0.8-1.1:1。
6. the method for modifying according to any one of claim 1-5, it is characterised in that step 2) in,
Reaction temperature is 20-80 DEG C, and the reaction time is 2-4h.
7. the method for modifying according to any one of claim 1-6, it is characterised in that step 3) in,
Baking temperature is 50-95 DEG C, and drying time is 2-4h.
8. a kind of usage right requires the modified cation-exchange resin that the method for modifying described in any one of 1-7 is obtained
The method comprehensively utilized to C-4-fraction after ether by catalyst, comprises the following steps：
Step i, after ether, C-4-fraction and acetic acid are reacted in the presence of nature-changed cation resin catalyst,
Obtain the sec-Butyl Acetate crude product containing acetic acid；
Step ii, water and the sec-Butyl Acetate crude product containing acetic acid are in the modified cation-exchange resin
There is hydrolysis in the presence of catalyst, in the mixture obtained from reaction, isolate sec-Butyl Acetate and Zhong Ding
The mixture of alcohol；
Step iii, carries out rectifying to the mixture of the sec-Butyl Acetate and sec-butyl alcohol, respectively obtains acetic acid Zhong Ding
Ester and sec-butyl alcohol product.
9. method according to claim 8, it is characterised in that in step i, carbon four evaporates after ether
C 4 olefin in point is 0.70-0.95 with the mol ratio of acetic acid, and the weight space velocity for mixing C-4-fraction is 1-3h-1。
10. method according to claim 8 or claim 9, it is characterised in that in step ii, in institute
State in step ii, the mol ratio of the sec-Butyl Acetate in water and sec-Butyl Acetate crude product is 1.0-1.5, acetic acid is secondary
The weight space velocity 1-3h of butyl ester-1。
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