CN109550520A - Tert-butyl alcohol dehydration prepares high-purity isobutylene catalyst, preparation method and its dehydration application - Google Patents
Tert-butyl alcohol dehydration prepares high-purity isobutylene catalyst, preparation method and its dehydration application Download PDFInfo
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- CN109550520A CN109550520A CN201811313898.2A CN201811313898A CN109550520A CN 109550520 A CN109550520 A CN 109550520A CN 201811313898 A CN201811313898 A CN 201811313898A CN 109550520 A CN109550520 A CN 109550520A
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 title claims abstract description 146
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 230000018044 dehydration Effects 0.000 title claims abstract description 38
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 15
- 238000004821 distillation Methods 0.000 claims abstract description 13
- 238000000746 purification Methods 0.000 claims abstract description 11
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 11
- 239000004088 foaming agent Substances 0.000 claims abstract description 6
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims abstract description 5
- 238000000605 extraction Methods 0.000 claims abstract description 3
- 239000000376 reactant Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 241001566735 Archon Species 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 22
- 239000012071 phase Substances 0.000 claims description 21
- 238000010792 warming Methods 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 210000003298 dental enamel Anatomy 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 229940037003 alum Drugs 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000036571 hydration Effects 0.000 abstract description 3
- 238000006703 hydration reaction Methods 0.000 abstract description 3
- 239000007943 implant Substances 0.000 abstract description 2
- 208000005156 Dehydration Diseases 0.000 abstract 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- 235000019504 cigarettes Nutrition 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- -1 isobutylene tert-butyl alcohol Chemical compound 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZQXSFZAMFNRZOQ-UHFFFAOYSA-N 2-methylpropan-2-ol;hydrate Chemical compound O.CC(C)(C)O ZQXSFZAMFNRZOQ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000009975 flexible effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J31/10—Ion-exchange resins sulfonated
-
- B01J35/56—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
- B01J37/24—Chlorinating
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- C07C2531/08—Ion-exchange resins
- C07C2531/10—Ion-exchange resins sulfonated
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
Present patent application provides a kind of tert-butyl alcohol dehydrations to prepare high-purity isobutylene catalyst, preparation method and its dehydration application.By styrene and divinylbenzene under pore-foaming agent and dispersing agent effect, aggregated, hole purification, chlorination and sulfonation prepare the catalyst.This catalyst in tert-butyl alcohol dehydration application is completed in fixed bed pre-reactor and catalytic distillation tower, 60~120 DEG C of reaction temperature, 0.5~2.0h of air speed in fixed bed pre-reactor‑1, 0.8~1.5MPa of pressure reaction, reactant enters catalytic distillation tower conversion zone, a feedback fixed bed pre-reactor of setting extraction gas phase at stripping section.The catalyst of the technical program has the advantages that sulfonate radical implant density is big, catalytic activity is high, sulfonate radical is stable and is difficult to fall off, the reaction temperature scope of application is wide, in practice it has proved that the application of this catalyst realizes the technical purpose of the tert-butyl alcohol hydration method production high-purity isobutylene of low energy consumption.
Description
Technical field
Present patent application is related to high molecular material preparation and its applied technical field more particularly to tert-butyl alcohol dehydration preparation is high
Polymer catalyst, preparation method and its application of purity isobutylene.
Background technique
Isobutene is a kind of important basic organic chemical industry raw material.It is particularly significant to obtain high-purity isobutylene, is mainly used for
Prepare a variety of Organic Chemicals such as butyl rubber, polyisobutene and methacrylate and fine chemicals.Currently, major stone
Oily company is all carrying out butyl rubber research, has huge potential demand to isobutene polymer grade, therefore, researchs and develops high-purity
Isobutene production technology is an extremely important technical task.The high-purity isobutene technology industrially applied at present mainly has methyl
Tertbutyl ether (MTBE) cracking process and tert-butyl alcohol dehydration method.The advantages of MTBE cracking process is product purity height, and device configuration is flexible
Property it is big, MTBE or isobutene can be produced according to the market demand, but the disadvantage is that because etherification method side reaction is more, it is different to obtain high-purity
Butylene, separation and purification technique is more complex, energy consumption is also big.Tert-butyl alcohol dehydration method is equally the master for obtaining high-purity isobutylene
Want technological approaches, have the advantages that process is simple, with low investment, side reaction is few, be easily isolated purification, product quality it is high, but, this skill
Art still fail to obtain the major technique of promotion and implementation the reason is that: tert-butyl alcohol dehydration react conversion per pass it is relatively low, in addition lack honest and clean
The tert-butyl alcohol raw material of valence.In recent years, rising year by year with tert-butyl alcohol yield has using Excess t-butanol dehydration preparing isobutene
Industry meaning.
Patent document CN104478644A discloses a kind of tert-butyl alcohol and prepares isobutene method, and scheme is by tert-butyl alcohol water
Solution and deionized water are passed through catalytic distillation tower, make tertiary butanol and water azeotropic mixture, de- during the tert-butyl alcohol passes through catalyst layer
Water generates isobutene, and the unreacted tert-butyl alcohol is absorbed by deionized water, reaches catalyst layer and continues dehydration generation isobutene.But
The reaction condition of this scheme is to promote the tert-butyl alcohol and water azeotropic, since the latent heat of vaporization of the tert-butyl alcohol and water is all very big, so energy consumption
It is very high；In addition, catalyst activity becomes by force with the raising of operating ambient temperature, water and tert-butyl alcohol conversion zone temperature are super in this programme
120 DEG C are crossed, but existing catalyst is difficult for long-term stable operation under the conditions of the temperature；Furthermore water is deposited always in reaction system
And export not in time, can inhibit reaction progress, cause tert-butyl alcohol conversion ratio relatively low.
Summary of the invention
The goal of the invention of present patent application is that raising tert-butyl alcohol conversion ratio, catalyst reaction Applicable temperature range are wider,
There is provided it is a kind of for obtain high-purity isobutylene tert-butyl alcohol dehydration prepare high-purity isobutylene catalyst, preparation method and its
Dehydration application, the catalyst that present patent application provides are anti-in the temperature that tert-butyl alcohol hydration method is dehydrated application production high-purity isobutylene
It answers condition wider, all there is high and stable reactivity in 90 DEG C or less and 90-120 DEG C of reaction temperature.
The tert-butyl alcohol dehydration that present patent application provides prepares high-purity isobutylene catalyst technology scheme, major technique
Content is: a kind of tert-butyl alcohol dehydration prepares high-purity isobutylene catalyst, by styrene and divinylbenzene in pore-foaming agent and
Under dispersing agent effect, aggregated, hole purification, chlorination and sulfonation are prepared:
1. polymerize
In stainless steel stirred tank with condensing unit, the suspension of styrene, divinylbenzene and pore-foaming agent and dispersing agent composition
Copolymerization system is warming up to 60-70 DEG C after aqueous phase dissolved, oily phase is added, and stirring is warming up to 80 DEG C -90 DEG C, speed of agitator 60-
120r/min reacts 8-10 hours, copolymer Archon is produced, wherein in parts by weight, the component of aqueous mixture includes: alum
20-40 parts, 20-30 parts of polyvinyl alcohol and 2500-3000 parts of water, the component of oil mixture include: 500-600 parts of styrene,
400-600 parts of divinylbenzene, 20-50 parts of C5-C7 alkane and 10-30 parts of benzoyl peroxide；Water phase and oil phase weight part ratio
For (2540-3070): (930-1280)；
2. the hole purifies
Deionized water decompression is boiled, and is repeatedly washed, is dried afterwards；
3. chlorination
Archon is placed in enamel stirred tank after the purification of hole, and chlorine, pressure 1.0-1.2MPa are passed through in kettle, is rolled and is reacted in stirring
2-4 hours；
4. sulfonation
Archon is handled through oleum sulfonation after chlorination, then under conditions of stirring and temperature are lower than 40 DEG C, deionized water is added dropwise
With into releasing again, repeatedly until liquid shows neutral.
The present patent application also provide a kind of systems realized the tert-butyl alcohol dehydration and prepare high-purity isobutylene catalyst
Preparation Method.
High-purity isobutylene catalyst is prepared using above-mentioned tert-butyl alcohol dehydration the present patent application also provide a kind of
Tert-butyl alcohol dehydration application, dehydration application apparatus include the fixed bed pre-reactor and catalytic distillation tower of expects pipe connection, fixed bed
The filling tert-butyl alcohol dehydration prepares high-purity isobutylene catalyst in pre-reactor and in catalytic distillation tower conversion zone, contains
The tert-butyl alcohol of water is pumped into pre-reactor by head tank and raw material pump and top feed pipeline, the condition in fixed bed pre-reactor
It is: 60~120 DEG C of temperature, 0.5~2.0h of Feed space velocities-1, pressure be 0.8~1.5MPa, reactants and products are liquid phase；It produces
Object enters catalytic distillation tower conversion zone top by bottom material discharge nozzle, and a side line of setting extraction gas phase, is connected to pre- at stripping section
On the top feed pipeline of reactor, the tower top pressure for controlling catalytic distillation tower is 0.3~0.5MPa, tower top temperature 40~60
DEG C, the extracted amount of the side line is the 0.05~0.3 of fresh feed amount.
Above-mentioned technical proposal preferably one of, fixed bed pre-reactor be dehydrated tert-butyl alcohol raw material water content be 10%-50%.
The best techniques of above-mentioned technical proposal are: the water content that fixed bed pre-reactor is dehydrated tert-butyl alcohol raw material is 10%-
40%。
The tert-butyl alcohol dehydration that present patent application provides prepares high-purity isobutylene catalyst, preparation method and its dehydration
Application technology scheme, catalyst have that sulfonate radical implant density is big, catalytic activity is high, sulfonate radical is stable and is difficult to fall off, instead
It answers temperature applicable range wide, all there is high and stable reactivity in 90 DEG C or less and 90-120 DEG C of reaction temperature, especially
It is to select C5-C7 alkane as pore-foaming agent, and molecule is greater than tert-butyl alcohol molecule, and obtained macropore polymerization Archon can be effective
Capture tert-butyl alcohol molecule, and be unlikely to allow that duct is excessive, diffusion is too fast and influences reaction speed, reaction generate isobutene and
Hydrone is smaller, is easy to spread out from duct, improves the conversion ratio of the tert-butyl alcohol, go on smoothly conducive to dehydration；Using
Catalyst simplifies the technique for applying method that tert-butyl alcohol dehydration prepares high-purity isobutylene, simple and easy, and tert-butyl alcohol conversion ratio
Height reaches 99.5% or more, and the purity is high of tower top isobutene is greater than 99%, and the tert-butyl alcohol hydration method production for realizing low energy consumption is high
The technical purpose of purity isobutylene.
Specific embodiment
It will illustrate the technical solution of present patent application, but the protection of present patent application by the expansion of following embodiment below
Range is not limited to given embodiment.
Embodiment 1
1. polymerize
In stainless steel stirred tank with reflux condensate device, water phase, by weight (the same below), the group subpackage of water phase is added
Include: 20 parts of alum, 30 parts of polyvinyl alcohol and 2500 parts of water, heating stirring is to being completely dissolved；60 DEG C are warming up to, oily phase is added,
In stirring, speed of agitator 110r/min, temperature are 80 DEG C of polymerization reactions 8 hours, the oil mutually include: 500 parts of styrene,
400 parts of divinylbenzene, 50 parts of pentane, 30 parts of benzoyl peroxide；
2. the hole purifies
Polymerizate is filtered, obtained polymer Archon is placed in 70 DEG C of deionized waters, is depressurized under the pressure of -0.090MPa
It boils 10 hours, then is washed with deionized 3 times, room temperature is dried；
3. chlorination
In enamel stirred tank, Archon after adding hole purification is passed through chlorine in kettle, and pressure control is 1.0MPa, rolls stirred tank
Reaction 4 hours；
4. sulfonation
The dry Archon after addition chlorination in another enamel stirred tank, control temperature in the kettle are lower than 65 DEG C, are added and send out in stirring
Cigarette sulfuric acid is warming up to thereafter 80 DEG C, reaction 2 hours to not having the Archon just, then is warming up to 100 DEG C, reaction 2 hours, most
After be warming up to 120 DEG C, reaction 4 hours, it is cooling, then in stirring, temperature lower than 40 DEG C in, deionized water, same is added dropwise into kettle
When release, repeatedly, until liquid shows neutral, obtain catalyst C1.
Embodiment 2
1. polymerize
In stainless steel stirred tank with reflux condensate device, water phase is added, the component of water phase includes: 30 parts of alum, polyethylene
30 parts of alcohol and 2700 parts of water, heating stirring is to being completely dissolved；70 DEG C are warming up to, adds oily phase, in stirring, speed of agitator is
110r/min, temperature be 85 DEG C polymerization reaction 8 hours, the oil mutually include: 600 parts of styrene, 600 parts of divinylbenzene,
50 parts of n-hexane, 10 parts of benzoyl peroxide；
2. the hole purifies
Polymerizate is filtered, obtained polymer Archon is placed in 70 DEG C of deionized waters, is depressurized under the pressure of -0.095MPa
It boils 8 hours, then is washed with deionized 3 times, room temperature is dried；
3. chlorination
In enamel stirred tank, Archon after adding hole purification is passed through chlorine in kettle, and pressure control is 1.2MPa, rolls stirred tank
Reaction 4 hours；
4. sulfonation
The dry Archon after addition chlorination in another enamel stirred tank, control temperature in the kettle are lower than 65 DEG C, are added and send out in stirring
Cigarette sulfuric acid is warming up to thereafter 80 DEG C, reaction 3 hours to not having the Archon just, then is warming up to 100 DEG C, reaction 2 hours, most
After be warming up to 120 DEG C, reaction 2 hours, it is cooling, then in stirring, temperature lower than 40 DEG C in, deionized water, same is added dropwise into kettle
When release, repeatedly, until liquid shows neutral, obtain catalyst C2.
Embodiment 3
1. polymerize
In stainless steel stirred tank with reflux condensate device, water phase is added, the component of water phase includes: 25 parts of alum, polyethylene
25 parts of alcohol and 3000 parts of water, heating stirring is to being completely dissolved；65 DEG C are warming up to, adds oily phase, in stirring, speed of agitator is
90r/min, temperature be 85 DEG C polymerization reaction 8 hours, the oil mutually includes: 550 parts of styrene, 500 parts of divinylbenzene, just
30 parts of heptane, 20 parts of benzoyl peroxide；
2. the hole purifies
Polymerizate is filtered, obtained polymer Archon is placed in 80 DEG C of deionized waters, is depressurized under the pressure of -0.090MPa
It boils 8 hours, then is washed with deionized 3 times, room temperature is dried；
3. chlorination
In enamel stirred tank, Archon after adding hole purification is passed through chlorine in kettle, and pressure control is 1.1MPa, rolls stirred tank
Reaction 3 hours；
4. sulfonation
The dry Archon after addition chlorination in another enamel stirred tank, control temperature in the kettle are lower than 65 DEG C, are added and send out in stirring
Cigarette sulfuric acid is warming up to thereafter 80 DEG C, reaction 2 hours to not having the Archon just, then is warming up to 100 DEG C, reaction 2 hours, most
After be warming up to 120 DEG C, reaction 2 hours, it is cooling, then in stirring, temperature lower than 40 DEG C in, deionized water, same is added dropwise into kettle
When release, repeatedly, until liquid shows neutral, obtain catalyst C3.
Embodiment 4
1. polymerize
In stainless steel stirred tank with reflux condensate device, water phase is added, the component of water phase includes: 30 parts of alum, polyethylene
20 parts of alcohol and 2800 parts of water, heating stirring is to being completely dissolved；60 DEG C are warming up to, adds oily phase, in stirring, speed of agitator is
120r/min, temperature be 90 DEG C polymerization reaction 10 hours, the oil mutually include: 500 parts of styrene, 400 parts of divinylbenzene,
20 parts of isoheptane, 10 parts of benzoyl peroxide；
2. the hole purifies
Polymerizate is filtered, obtained polymer Archon is placed in 70 DEG C of deionized waters, is depressurized under the pressure of -0.090MPa
It boils 8 hours, then is washed with deionized 3 times, room temperature is dried；
3. chlorination
In enamel stirred tank, Archon after adding hole purification is passed through chlorine in kettle, and pressure control is 1.0MPa, rolls stirred tank
Reaction 3 hours；
4. sulfonation
The dry Archon after addition chlorination in another enamel stirred tank, control temperature in the kettle are lower than 65 DEG C, are added and send out in stirring
Cigarette sulfuric acid is warming up to thereafter 80 DEG C, reaction 3 hours to not having the Archon just, then is warming up to 100 DEG C, reaction 3 hours, most
After be warming up to 120 DEG C, reaction 4 hours, it is cooling, then in stirring, temperature lower than 40 DEG C in, deionized water, same is added dropwise into kettle
When release, repeatedly, until liquid shows neutral, obtain catalyst C4.
The above various embodiments catalyst prepares the dehydration application of high-purity isobutylene in tert-butyl alcohol dehydration, will be contained by raw material pump
The water tert-butyl alcohol is sent into the fixed bed pre-reactor equipped with filling the above various embodiments catalyst by head tank, then through catalytic distillation tower
Dehydration, and a side line of gas phase is extracted in setting out at the stripping section of catalytic distillation tower, is connected to the top feed of pre-reactor
On pipeline, overhead line obtains high-purity isobutylene through condenser, catalyst charge in the fixed bed pre-reactor in evaluation
Catalyst charge for 40ml, catalytic distillation tower is 100ml, and wherein the dehydration tert-butyl alcohol raw material of embodiment a, b, c, d contains
Water is respectively as follows: 10%, 25%, 30%, 40%, and respectively corresponds the catalyst using above 4 embodiments, and evaluation assessment value is shown in
Following table:
The total conversion of the tert-butyl alcohol in table is greater than 99.5%, and tower top isobutene purity is greater than 99%.For water content be greater than 40%,
Dehydration tert-butyl alcohol raw material no more than 50% also has same technical effect.
Claims (5)
1. a kind of tert-butyl alcohol dehydration prepares high-purity isobutylene catalyst, which is characterized in that by styrene and divinylbenzene
Under pore-foaming agent and dispersing agent effect, aggregated, hole purification, chlorination and sulfonation are prepared:
1. polymerize
In stainless steel stirred tank with condensing unit, the suspension of styrene, divinylbenzene and pore-foaming agent and dispersing agent composition
Copolymerization system is warming up to 60-70 DEG C after aqueous phase dissolved, oily phase is added, and stirring is warming up to 80 DEG C -90 DEG C, speed of agitator 60-
120r/min reacts 8-10 hours, copolymer Archon is produced, wherein in parts by weight, the component of aqueous mixture includes: alum
20-40 parts, 20-30 parts of polyvinyl alcohol and 2500-3000 parts of water, the component of oil mixture include: 500-600 parts of styrene,
400-600 parts of divinylbenzene, 20-50 parts of C5-C7 alkane and 10-30 parts of benzoyl peroxide；Water phase and oil phase weight part ratio
For (2540-3070): (930-1280)；
2. the hole purifies
Deionized water decompression is boiled, and is repeatedly washed, is dried afterwards；
3. chlorination
Archon is placed in enamel stirred tank after the purification of hole, and chlorine, pressure 1.0-1.2MPa are passed through in kettle, is rolled and is reacted in stirring
2-4 hours；
4. sulfonation
Archon is handled through oleum sulfonation after chlorination, then under conditions of stirring and temperature are lower than 40 DEG C, deionized water is added dropwise
With into releasing again, repeatedly until liquid shows neutral.
2. the preparation method that a kind of tert-butyl alcohol dehydration described in claim 1 prepares high-purity isobutylene catalyst.
3. a kind of tert-butyl alcohol dehydration described in claim 1 prepares the tert-butyl alcohol dehydration application of high-purity isobutylene catalyst,
It is characterized in that, it is dehydrated the fixed bed pre-reactor (3) and catalytic distillation tower (4) that applied system equipment includes expects pipe connection,
The filling tert-butyl alcohol dehydration prepares high-purity isobutyl in fixed bed pre-reactor (3) and in catalytic distillation tower (4) conversion zone
Alkene catalyst, the aqueous tert-butyl alcohol are pumped into pre-reactor (3) by head tank (1) and raw material pump (2) and top feed pipeline, Gu
Condition in fixed bed pre-reactor (3) is: 60~120 DEG C of temperature, 0.5~2.0h of Feed space velocities-1, pressure be 0.8~1.5MPa,
Reactants and products are liquid phase；Fixed bed pre-reactor (3) product enters catalytic distillation tower (4) conversion zone by bottom discharge pipe
Top, a side line (6) for setting extraction gas phase, is connected on the top feed pipeline of pre-reactor (3), control is urged at stripping section
The tower top pressure for changing destilling tower (4) is 0.3~0.5MPa, 40~60 DEG C of tower top temperature, the extracted amount of the side line be it is fresh into
The 0.05~0.3 of doses.
4. dehydration application according to claim 3, which is characterized in that fixed bed pre-reactor (4) is dehydrated tert-butyl alcohol raw material
Water content be 10%-50%.
5. dehydration application according to claim 4, which is characterized in that fixed bed pre-reactor dehydration tert-butyl alcohol raw material contains
Water is 10%-40%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724034A (en) * | 2019-09-24 | 2020-01-24 | 南京金陵亨斯迈新材料有限责任公司 | Method for relieving residual liquid blockage of molybdenum-containing catalyst in tertiary butanol refining process |
| CN112705266A (en) * | 2021-01-26 | 2021-04-27 | 丹东明珠特种树脂有限公司 | Catalyst for preparing methyl methacrylate, preparation method and esterification preparation process thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1151334A (en) * | 1995-12-02 | 1997-06-11 | 中国石化齐鲁石油化工公司 | Method for prepn. of catalyst of large porous strong acid cation exchange resin |
| CN1609082A (en) * | 2003-06-17 | 2005-04-27 | 奥克森诺奥勒芬化学股份有限公司 | Process for preparing isobutene from tertiary butanol |
| CN103509149A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method of cation exchange resin with high-temperature thermostability |
| CN103506158A (en) * | 2013-10-25 | 2014-01-15 | 凯瑞化工股份有限公司 | Catalyst applicable to reaction in production of isobutene through tertiary butanol dehydration and preparation method thereof |
| US20150307413A1 (en) * | 2009-09-24 | 2015-10-29 | Signa Chemstry, Inc. | Catalytic dehydration of alcohols using non-volatile acid catalysts |
| CN108371956A (en) * | 2018-01-10 | 2018-08-07 | 山东滨州裕华化工厂有限公司 | A kind of preparation method of catalyst of large porous strong acid cation exchange resin |
-
2018
- 2018-11-06 CN CN201811313898.2A patent/CN109550520A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1151334A (en) * | 1995-12-02 | 1997-06-11 | 中国石化齐鲁石油化工公司 | Method for prepn. of catalyst of large porous strong acid cation exchange resin |
| CN1609082A (en) * | 2003-06-17 | 2005-04-27 | 奥克森诺奥勒芬化学股份有限公司 | Process for preparing isobutene from tertiary butanol |
| US20150307413A1 (en) * | 2009-09-24 | 2015-10-29 | Signa Chemstry, Inc. | Catalytic dehydration of alcohols using non-volatile acid catalysts |
| CN103509149A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method of cation exchange resin with high-temperature thermostability |
| CN103506158A (en) * | 2013-10-25 | 2014-01-15 | 凯瑞化工股份有限公司 | Catalyst applicable to reaction in production of isobutene through tertiary butanol dehydration and preparation method thereof |
| CN108371956A (en) * | 2018-01-10 | 2018-08-07 | 山东滨州裕华化工厂有限公司 | A kind of preparation method of catalyst of large porous strong acid cation exchange resin |
Non-Patent Citations (2)
| Title |
|---|
| 化学工业部科学技术情报研究所: "《化工产品手册 有机化工原料 上》", 28 February 1985, 北京：化学工业出版社 * |
| 邓佩鑫等: "离子交换树脂法分离异丁烯工艺的工业化", 《石油化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110724034A (en) * | 2019-09-24 | 2020-01-24 | 南京金陵亨斯迈新材料有限责任公司 | Method for relieving residual liquid blockage of molybdenum-containing catalyst in tertiary butanol refining process |
| CN110724034B (en) * | 2019-09-24 | 2022-02-22 | 南京金陵亨斯迈新材料有限责任公司 | Method for relieving residual liquid blockage of molybdenum-containing catalyst in tertiary butanol refining process |
| CN112705266A (en) * | 2021-01-26 | 2021-04-27 | 丹东明珠特种树脂有限公司 | Catalyst for preparing methyl methacrylate, preparation method and esterification preparation process thereof |
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