CN106478375A - A kind of method that vicinal diamines class compound is synthesized for catalyst with anion exchange resin - Google Patents
A kind of method that vicinal diamines class compound is synthesized for catalyst with anion exchange resin Download PDFInfo
- Publication number
- CN106478375A CN106478375A CN201510526392.XA CN201510526392A CN106478375A CN 106478375 A CN106478375 A CN 106478375A CN 201510526392 A CN201510526392 A CN 201510526392A CN 106478375 A CN106478375 A CN 106478375A
- Authority
- CN
- China
- Prior art keywords
- exchange resin
- formula
- catalyst
- anion exchange
- class compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000003957 anion exchange resin Substances 0.000 title claims abstract description 21
- 150000004985 diamines Chemical class 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 150000002118 epoxides Chemical class 0.000 claims abstract description 11
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical class 0.000 claims abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 5
- -1 hydro carbons Epoxide Chemical class 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 239000003456 ion exchange resin Substances 0.000 claims description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 claims 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 abstract description 4
- 229920003053 polystyrene-divinylbenzene Polymers 0.000 abstract description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- XLMFDCKSFJWJTP-UHFFFAOYSA-N pentane-2,3-diol Chemical compound CCC(O)C(C)O XLMFDCKSFJWJTP-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07C29/10—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 ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—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 ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
- C07C29/106—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 ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
-
- 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
-
- 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
- B01J2231/48—Ring-opening reactions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method that vicinal diamines class compound is synthesized for catalyst with anion exchange resin.The method, with epoxide of hydrocarbon kind as raw material, with anion exchange resin as catalyst, prepares vicinal diamines class compound using fixed bed continuous hydrolysis reaction process；Described anion exchange resin is the macroporous polystyrene-divinylbenzene quaternary of halogen substiuted from anion exchange resin.This synthetic method is simple, and catalyst can repeatedly utilize, and feed stock conversion is high, and vicinal diamines class compound yield is high.
Description
Technical field
The invention belongs to synthesis chemical technology field, specifically, it is related to a kind of method that vicinal diamines class compound is synthesized for catalyst with anion exchange resin.
Background technology
Vicinal diamines class compound such as 1,2- pentanediol, 1,2- ring pentanediol, 1,2- Hexalin, 2,3- pentanediol etc. are class important chemical, have important purposes in fields such as medicine, pesticide, surfactants.The more commonly used synthetic method of adjacent dibastic alcohol compound is that olefin hydrocarbon oxidation reaction is generated epoxide, and then hydrolysis generate corresponding vicinal diamines again.Chinese patent CN103992207A discloses with kind of " methods for hydrogen peroxide/cation exchange resin system catalysis oxidation alkene vicinal diamines ", this Patent technology characteristic is with the element modified cation exchange resin of Ag, Mn, K, Co, Fe as catalyst, aqueous hydrogen peroxide solution is oxygen source, and olefin oxidation is become vicinal diamines by one-step method.But, the catalyst service life of this patent specification description is shorter, usually applies mechanically 15 times it is clear that the promotion and application of this this technology of defective effect.Chinese invention patent CN101018752A discloses the method for producing unsaturated vicinal diol compound, it is characterized in that with the epoxide containing unsaturated bond as reaction raw materials, with containing VB, VI B race vanadium, molybdenum, wolfram element silicate as catalyst, obtain corresponding unsaturated vicinal dibastic alcohol compound by hydrolysis, target product reaction yield is 80%～95%, and by-product is 5%～10%.
Content of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of method that vicinal diamines class compound is synthesized for catalyst with anion exchange resin.This simple synthetic method, catalyst can repeatedly utilize, and feed stock conversion is high, and vicinal diamines class compound yield is high.
The present invention provides a kind of method synthesizing vicinal diamines class compound for catalyst with anion exchange resin, it is with epoxide of hydrocarbon kind as reaction raw materials, under anion-exchange resin catalyst catalytic action, vicinal diamines class compound is prepared using fixed bed continuous hydrolysis reaction process；Wherein：Described anion-exchange resin catalyst is the macroporous polystyrene divinylbenzene quaternary ammonium anion exchange resin of halogen para-orientation, and its degree of cross linking is 1%～10%, and resin butt base exchange capacity is 3.5～4.2mmol.g-1,
In the present invention, the macroporous polystyrene-divinylbenzene quaternary ammonium anion exchange resin of described halogen para-orientation, shown in its structure such as formula (3)：
Wherein：1,2,3,4,5,6 represents halogen for carbon atoms on a benzene ring numbering, X, is connected with the carbon atoms on a benzene ring that numbering is 4, y represents 1～10 integer, and m, n are positive integer, m：N=1:10～1：100, R5、R6、R7In methyl, ethyl, propyl group, butyl, amyl group or hexyl any one, quaternary ammonium salt ionic group R5R6R7N+(CH2) number in y and phenyl ring be 2,3,5,6 carbon atom in any one be connected, form the ion exchange resin of corresponding two kinds of different structures or the mixture of both resins, be usually formed as the mixture of both different structures；MK-Represent anion, it is selected from any one in hydroxyl, formate, acetate, propionate, butanoic acid root, pentanoate, oxalate, malonate or bicarbonate radical, and K is the quantivalence of anion, is 1 or 2.
In the present invention, described epoxide of hydrocarbon kind has structure shown in formula (2)；The vicinal diamines class compound obtaining has structure shown in formula (1)；
Wherein：R in formula (1) and formula (2)1、R2、R3、R4Independent in hydrogen, the straight chained alkyl of C1～C14, branched alkyl or cycloalkyl any one.
In the present invention, described anion is formate, acetate or bicarbonate radical.
In the present invention, X described in formula (3) is Br or Cl.
In the present invention, the ion exchange resin degree of cross linking represented by formula (3) is 2%～5%.
The reaction equation of the present invention is shown below：
Wherein, R1、R2、R3、R4Independent selected from hydrogen, alkyl or cycloalkyl；Preferably, R1、R2、R3、R4Independent in hydrogen, the straight chained alkyl of C1～C14, branched alkyl or cycloalkyl any one.
In the present invention, in described fixed bed continuous hydrolysis reaction process, hydrolysising reacting temperature controls at 80～130 DEG C, and reaction pressure controls in 1.5MPa～2.0MPa, and the epoxide mass percent concentration entering reactor is 5%～50%, and volume space velocity is 0.1～1h-1.Preferably, the epoxide mass percent concentration entering reactor is 20%～50%, and volume space velocity is 0.2～0.5h-1.
The beneficial effects of the present invention is：
(1) ion exchange resin general work temperature is less than 120 DEG C, and in use because resin easily expands fragmentation, active group is lost, and so that catalyst is inactivated；And the anion exchange resin in the present invention is high temperature resistant, active good, expansion rate is less；
(2) this synthetic method is simple, and catalyst remains in that good catalytic performance under the conditions of long-term operation, and feed stock conversion is high, and vicinal diamines class compound yield is high；Its epoxide of hydrocarbon kind conversion ratio 99.1%～99.8%, adjacent diol reaction yield 90.1%～93.7%.
Specific embodiment
Hereinafter the present invention is illustrated with embodiment, but the invention is not limited in embodiment.
First, conversion ratio and reaction yield computing formula are as follows
2nd, the preparation of vicinal diamines class compound
(1) first with the monoolefine of C2～C16 as raw material, it is catalyst using the titanium-silicon molecular sieve TS-1 with MFI structure or HTS-1, with aqueous hydrogen peroxide solution as oxidant, first monoolefine is oxidized to corresponding epoxide of hydrocarbon kind according to technique disclosed in CN104211665A；
(2) in 100ml jacket type rustless steel tubular reactor, load structure, halogen substiuted macroporous polystyrene quaternary ammonium anion exchange resin catalyst shown in 30ml formula (3), beds upper and lower side loads inertia bique ball.The temperature of reactor is controlled by outer circulation type conduction oil, reactor pressure is controlled by the counterbalance valve being arranged on discharging opening pipeline, reaction mass is entered by reactor bottom through dosing pump, flows through beds and is flowed out by reactor head, flows into product storage tank after cooled device cooling.Timing sampling, gas chromatographic analysiss product forms.Investigate reaction raw materials concentration, reaction temperature, pressure, liquid hourly space velocity (LHSV) and catalyst type and change to the impact reacted, the reaction raw materials used by embodiment 1～10 are shown in Table 1, and catalyst used has formula (3) structure, wherein X, y, R5, R6, R7Group, resin's crosslinkage, resin base exchange capacity (butt) is shown in Table 2, and reaction process condition and reaction result are shown in Table 3., to prepare for reaction raw materials to halogenated styrenes, benzene divinyl, reaction equation is as follows for catalyst shown in formula (3) structure：
Embodiment【1～10】
Table 1
Table 2
Table 3
Claims (8)
1. a kind of method with anion exchange resin for catalyst synthesis vicinal diamines class compound is it is characterised in that it is with hydro carbons
Epoxide is reaction raw materials, under anion-exchange resin catalyst catalytic action, reacts work using fixed bed continuous hydrolysis
Skill prepares vicinal diamines class compound；Wherein：Described anion-exchange resin catalyst is that the macropore of halogen para-orientation gathers
Styrene-divinylbenzene quaternary ammonium anion exchange resin, its degree of cross linking is 1%～10%, and resin butt alkali exchanges and holds
Measure as 3.5～4.2mmol.g-1.
2. method according to claim 1 is it is characterised in that the macroporous polystyrene-divinyl of described halogen para-orientation
Shown in the structure such as formula (3) of base benzene quaternary ammonium anion exchange resin：
Wherein：1,2,3,4,5,6 is carbon atoms on a benzene ring numbering, and X represents halogen, with phenyl ring in number be 4 carbon atom
It is connected, y represents 1～10 integer, m, n are positive integer, m：N=1:10～1：100, R5、R6、R7Selected from first
In base, ethyl, propyl group, butyl, amyl group or hexyl any one, quaternary ammonium salt ionic group R5R6R7N+(CH2) y with
Numbering in phenyl ring is that any one in 2,3,5,6 carbon atoms is connected, and forms corresponding two kinds of different structures
Ion exchange resin or the mixture of both resins, are usually formed the mixture of both different structures；MK-Represent cloudy from
Son, it is selected from hydroxyl, formate, acetate, propionate, butanoic acid root, pentanoate, oxalate, malonate or carbon
In sour hydrogen radical any one, K be anion quantivalence, be 1 or 2.
3. method according to claim 1 it is characterised in that：Described epoxide of hydrocarbon kind has shown in formula (2)
Structure；The vicinal diamines class compound obtaining has structure shown in formula (1)；
Wherein：R in formula (1) and formula (2)1、R2、R3、R4The independent straight chain selected from hydrogen, C1～C14
In alkyl, branched alkyl or cycloalkyl any one.
4. method according to claim 1 is it is characterised in that described anion is formate, acetate or bicarbonate radical.
5. method according to claim 1 is it is characterised in that in formula (3), described X is Br or Cl.
6. method according to claim 1 is it is characterised in that the macropore of halogen para-orientation represented by formula (3) gathers
The degree of cross linking of styrene quaternary ammonium anion exchange resin is 2%～5%.
7. method according to claim 1 is it is characterised in that in described fixed bed continuous hydrolysis reaction process, hydrolysis
At 80～130 DEG C, reaction pressure controls in 1.5MPa～2.0MPa temperature control, enters the epoxy compound amount of substance hundred of reactor
Specific concentration is divided to be 5%～50%, volume space velocity is 0.1～0.8h-1.
8. method according to claim 7 is it is characterised in that in described fixed bed continuous hydrolysis reaction process, enter reactor
Epoxide mass percent concentration be 20%～50%, volume space velocity be 0.2～0.5h-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510526392.XA CN106478375A (en) | 2015-08-25 | 2015-08-25 | A kind of method that vicinal diamines class compound is synthesized for catalyst with anion exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510526392.XA CN106478375A (en) | 2015-08-25 | 2015-08-25 | A kind of method that vicinal diamines class compound is synthesized for catalyst with anion exchange resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106478375A true CN106478375A (en) | 2017-03-08 |
Family
ID=58233038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510526392.XA Pending CN106478375A (en) | 2015-08-25 | 2015-08-25 | A kind of method that vicinal diamines class compound is synthesized for catalyst with anion exchange resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106478375A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109718853A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of supported solid heteropolyacid catalyst and preparation method thereof for epoxidation reaction of olefines |
| CN109718854A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of solid acid catalysts and the preparation method and application thereof |
| CN116020557A (en) * | 2021-10-25 | 2023-04-28 | 中国石油化工股份有限公司 | Ion exchange resin catalyst, preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1139916A (en) * | 1994-01-31 | 1997-01-08 | 国际壳牌研究有限公司 | Process for the preparation of alkylene glycols |
| CN1198429A (en) * | 1997-04-30 | 1998-11-11 | 三菱化学株式会社 | Process for producing alkylene glycol |
| CN1333740A (en) * | 1998-12-14 | 2002-01-30 | 国际壳牌研究有限公司 | Quaternary phosphonium salt catalysts in catalytic hydrolsysi of alkylene oxides |
| CN1513597A (en) * | 2003-07-18 | 2004-07-21 | 中国石油化工股份有限公司 | Anion-exchange resin catalyst for ethylene oxide hydration reaction and preparing process |
| CN101229520A (en) * | 2008-01-30 | 2008-07-30 | 烟台大学 | Modified cation exchange resin catalyst |
| CN101821002A (en) * | 2007-10-15 | 2010-09-01 | 科学设计有限责任两合公司 | Solid catalyst useful for converting alkylene oxide to alkylene glycol |
-
2015
- 2015-08-25 CN CN201510526392.XA patent/CN106478375A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1139916A (en) * | 1994-01-31 | 1997-01-08 | 国际壳牌研究有限公司 | Process for the preparation of alkylene glycols |
| CN1198429A (en) * | 1997-04-30 | 1998-11-11 | 三菱化学株式会社 | Process for producing alkylene glycol |
| CN1333740A (en) * | 1998-12-14 | 2002-01-30 | 国际壳牌研究有限公司 | Quaternary phosphonium salt catalysts in catalytic hydrolsysi of alkylene oxides |
| CN1513597A (en) * | 2003-07-18 | 2004-07-21 | 中国石油化工股份有限公司 | Anion-exchange resin catalyst for ethylene oxide hydration reaction and preparing process |
| CN101821002A (en) * | 2007-10-15 | 2010-09-01 | 科学设计有限责任两合公司 | Solid catalyst useful for converting alkylene oxide to alkylene glycol |
| CN101229520A (en) * | 2008-01-30 | 2008-07-30 | 烟台大学 | Modified cation exchange resin catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 孙富安 等: "聚（邻氯苯乙烯-二乙烯基苯）强酸性阳离子交换树脂催化丁烯水合工艺", 《离子交换与吸附》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109718853A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of supported solid heteropolyacid catalyst and preparation method thereof for epoxidation reaction of olefines |
| CN109718854A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of solid acid catalysts and the preparation method and application thereof |
| CN116020557A (en) * | 2021-10-25 | 2023-04-28 | 中国石油化工股份有限公司 | Ion exchange resin catalyst, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104248968A (en) | Catalyst for preparation of propylene by direct dehydrogenation of propane and preparation method thereof | |
| KR20170012217A (en) | Apparatus and method for producing cyclic carbonate | |
| CN106478375A (en) | A kind of method that vicinal diamines class compound is synthesized for catalyst with anion exchange resin | |
| BR112012014674B1 (en) | Process for the production of olefin oxide, catalyst, and its use | |
| CN106478374A (en) | A kind of method that vicinal diamines class compound is prepared by ring-opening reaction | |
| RU2015123993A (en) | A FLOW-FLOW REACTOR WITH A PSEU-LIQUID CATALYST LAYER FOR OLEFIN DEGHODATION | |
| CN102391084A (en) | Method for preparing benzaldehyde by catalytic oxidation of phenylcarbinol | |
| CN106669683B (en) | A kind of hud typed amorphous silicon Al catalysts and its preparation method and application | |
| CN106478373A (en) | A kind of method that vicinal diamines class compound is synthesized for catalyst with macroporous anion exchange resin | |
| CN106478372A (en) | A kind of method that utilization quaternary salt type anion exchange resin prepares vicinal diamines class compound | |
| CN103623848B (en) | A kind of composite mesoporous metal oxide catalyst preparation method | |
| CN106478371A (en) | A kind of method with epoxide of hydrocarbon kind as Material synthesis vicinal diamines class compound | |
| CN101279892B (en) | Method for preparing 1,2-cyclohexanediol by catalytic oxidation of cyclohexene | |
| CN106478365A (en) | A kind of synthetic method of vicinal diamines class compound | |
| CN104844539B (en) | A kind of preparation method of piperidines | |
| CN107628933A (en) | A kind of continuous production technology that the acetone of 1 methoxyl group 2 is synthesized by the propyl alcohol direct dehydrogenation of 1 methoxyl group 2 | |
| CN109970554A (en) | The method that (methyl) acrylic acid is directly appended to biological base oil | |
| CN104387235B (en) | Method for synthesizing prenol employing selective hydrogenation of 3-methylcrotonaldehyde | |
| CN104209144B (en) | The preparation method of a kind of catalyst system and catalyzing and preparation method thereof and vinylacetylene | |
| CN105854916B (en) | A kind of palladium carbon catalyst and its preparation process of calcium carbonate cladding | |
| CN109721568A (en) | A kind of method of solid acid catalysis oxyalkylene | |
| CN117586089A (en) | Method for preparing alkylate by micro-channel reactor | |
| CN107311839B (en) | The fluoro- chlorine exchange system of gas phase for seven fluorine cyclopentene method | |
| CN105251507B (en) | Use AgO/CuO-MgO-SiO2The method of four component composite oxide catalysts catalysis ethanol butadiene | |
| CN1326820C (en) | Method for producing lower alcohol continuously |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170308 |
|
| RJ01 | Rejection of invention patent application after publication |