CN110003140A - The synthesis of epoxychloropropane and the device and method of catalyst on-line regeneration - Google Patents
The synthesis of epoxychloropropane and the device and method of catalyst on-line regeneration Download PDFInfo
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- CN110003140A CN110003140A CN201910343916.XA CN201910343916A CN110003140A CN 110003140 A CN110003140 A CN 110003140A CN 201910343916 A CN201910343916 A CN 201910343916A CN 110003140 A CN110003140 A CN 110003140A
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- kettle
- catalyst
- dope
- regeneration
- epoxychloropropane
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- 239000003054 catalyst Substances 0.000 title claims abstract description 263
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 230000008929 regeneration Effects 0.000 title claims abstract description 79
- 238000011069 regeneration method Methods 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 54
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 31
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 158
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims abstract description 41
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 83
- 239000012528 membrane Substances 0.000 claims description 80
- 239000002904 solvent Substances 0.000 claims description 69
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 68
- 238000002156 mixing Methods 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 230000009719 regenerative response Effects 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 230000036961 partial effect Effects 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- VIRPUNZTLGQDDV-UHFFFAOYSA-N chloro propanoate Chemical compound CCC(=O)OCl VIRPUNZTLGQDDV-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 239000002351 wastewater Substances 0.000 abstract description 12
- 239000001110 calcium chloride Substances 0.000 abstract description 5
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 4
- 230000001681 protective effect Effects 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 238000005265 energy consumption Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000006735 epoxidation reaction Methods 0.000 description 7
- 238000010924 continuous production Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical group ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- MZPBNFLTHBUURE-UHFFFAOYSA-N C=CC.[Cl] Chemical group C=CC.[Cl] MZPBNFLTHBUURE-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- MPSXZBZUSOMAQW-UHFFFAOYSA-N acetic acid;prop-1-ene Chemical group CC=C.CC(O)=O MPSXZBZUSOMAQW-UHFFFAOYSA-N 0.000 description 2
- -1 alkene Propyl chloride Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 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 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000013459 approach Methods 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
- 239000003225 biodiesel Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 229960003711 glyceryl trinitrate Drugs 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The synthesis of epoxychloropropane and the device and method of catalyst on-line regeneration, described device include reaction kettle, N set wash kettle and regeneration kettle, N >=2.The method includes the synthesis of epoxychloropropane, the on-line cleaning of catalyst and the regeneration of catalyst.Apparatus of the present invention structure is simple, catalyst can on-line regeneration, the long service life of catalyst is at low cost, is suitable for industrialized production；The method of the present invention chloropropene conversion ratio and to product selectivity height, the long service life of catalyst, use cost is low, and reaction condition is mild, and wastewater discharge is less, and waste water COD is low, and no intractable calcium chloride solid generates, environmentally protective.
Description
Technical field
Present invention relates particularly to a kind of synthesis of epoxychloropropane and the device and methods of catalyst on-line regeneration.
Background technique
Epoxychloropropane is a kind of important Organic Chemicals and fine chemical product, and purposes is very extensive.It is with it
Epoxy resin made from raw material is strong with caking property, resistant to chemical media burn into chemical stability is good, excellent in cushion effect and Jie
The features such as matter excellent electrical property, has extensive in industries such as coating, adhesive, reinforcing material, cast material and electronics laminates
Application.In addition, epoxychloropropane can also be used in synthetic glycerine, nitroglycerine, glass reinforced plastic, electrical isolation product, surface-active
A variety of productions such as agent, medicine, pesticide, coating, sizing material, ion exchange resin, plasticizer, (contracting) glycerol derivatives, chlorohydrin rubber
Product, as cellulose esters, resin, cellulose ether solvent, for producing chemical stabilizer, chemical dyestuff and water treatment agent etc..
The production of epoxychloropropane starts from the thirties in last century.1945, Shell Chemical Co started chlorohydrination (or alkene
Propyl chloride method, chloropropene method) industrialized production；Nineteen fifty-five, it is high that Dow Chemical becomes the 2nd household propylene in the world
The manufacturer of warm chloridising production epoxychloropropane；1985, Japanese Showa electrician company start using acetate propylene ester process (or
Claim allyl acetate-allyl alcohol method) epoxychloropropane is produced, the same year realizes the industrialization of the method；DOW Chemical in 2006, Su Wei declaration are built up simultaneously
The glycerol method epoxychloropropane large production equipment gone into operation rapidly.Currently, the production technology of industrial epoxychloropropane mainly has
Three of the above method, it is specific as follows.
(1) propylene high-temperature chloridising:
Advantage: 1) technical maturity, stable operation；2) introduction expense is low, and plant investment expense is low compared with acetate propylene rouge method；3) intermediate
Product chloropropene can be used for producing pesticide, resin etc..It can be according to market situation, in chloropropene and epoxychloropropane in actual production
It is adjusted between two kinds of products, balanced production.
Disadvantage: 1) reaction by-product is more, and raw material conversion ratio is low, and the norm quota of consumption is higher；2) equipment seriously corroded, energy consumption
It is higher；3) quantity of wastewater effluent is larger.
(2) acetate propylene rouge method:
Advantage: 1) acetyl chlorination technique is used, high income, consumption of raw materials is low；2) product quality is higher, purity is high；3) it avoids
High-temperature chlorination, reaction condition mitigate, stable operation, and propylene consumption is reduced, Ca (OH)2And the consumption of chlorine is decreased by almost one
Half；4) byproduct of reaction and contain CaCl2The discharge amount of waste water all greatly reduces.
Disadvantage: 1) reaction step is more, and process route is long and complex, still has a large amount of saponification waste-water to need to discharge；2) system
In have acetic acid, stainless steel equipment need to be used；3) oxidation reactor is bulky, expensive catalyst and cannot regenerate；4) in reaction
Oxygen, circulating air (oxygenous, propylene etc.) compressed gas is added, it is necessary to pay much attention to the peace of the anti-Mixed Gases Explosion of propenyl unit
Full reliability.
(3) glycerin chlorination method:
Advantage: 1) process flow is short, and reactor part is not required to run in the condition of high temperature, invests low；2) biodiesel byproduct is utilized
Object glycerol, raw materials for production cost are relatively low；3) by-product is few, and waste processing cost is low, and operating condition is mild, safe.
Disadvantage: 1) production time is short, lack of experience；2) industry glycerol price is high, is only capable of using by-product glycerol as raw material.
CN101747297A discloses a kind of method of continuous production epoxychloropropane, and this method is by chlorallylene, mistake
Hydrogen oxide and solvent introduce multiple fixed bed reactors equipped with titanium-silicon molecular sieve catalyst, make chlorallylene and hydrogen peroxide into
Row epoxidation reaction；Stop epoxidation reaction at least one fixed bed reactors, by catalyst regeneration therein, wherein
Any one reactor has epoxidation anti-when carrying out the regeneration of catalyst at least one reactor in other reactors
Should carry out.Although epoxychloropropane production process may be implemented this process simplify the separation process of catalyst and reaction product
Long period continuous and steady operation, reduce loss caused by equipment is stopped work, technical process is simple, and it is convenient that process is realized.But
In pelletized form or column, particle is big, and specific surface area of catalyst is small for catalyst used in this method, and activity is not high, and with using
Time extension, activity decline when regeneration effect is bad, need to stop tower maintenance replacement raw catelyst, and ability holding meanss production is flat
Weighing apparatus can not achieve catalyst on-line regeneration and recycle.
CN101486690A discloses a kind of chloro propylene epoxidation and prepares ECH(epoxychloropropane) method, be by chlorine third
Alkene, solvent and titanium-silicon molecular sieve catalyst fine grained are put into reaction kettle, and at 10~80 DEG C, hydrogen peroxide is added；Reaction is weak
It is carried out under acid condition, reacting rear material carries out grease layering through pans, is divided into oily phase and water phase；It is oily to be mutually sent into rectifying column point
From chloropropene and ECH, water phase is after filtering, and catalyst cake is by solvent washing, regeneration or directly with solvent mashing rear enclosure
For epoxidation reaction, filtered water layer chloropropene extracts ECH therein, extraction oil reservoir and the separating obtained oil reservoir of reaction solution
Merge rectifying, or extraction oil reservoir is applied in epoxidation reaction；Raffinate crystal evaporate recycles methanol, and set is used for the preparation of catalyst.Though
Right this method process is simple, and solvent usage is few, and reaction product separation yield is high, is easy to realization of industrialization, still, this method does not have
It realizes continuous production, be also not carried out the continuous on-line regeneration of catalyst and recycle.
CN107033107A discloses a kind of method for preparing epoxychloropropane, is in slurry bed system slaking reaction device outer circulation
Pipeline on, be added catalyst, pH adjusting agent, solvent, three through in level-one static mixer mix after, then at pipeline reactor
Chloropropene, the hydrogen peroxide of interior addition carry out chloro propylene epoxidation homogeneous catalytic reaction, through cooler cooling, second level static mixer
Mix, into slurry bed system slaking reaction device in carry out slaking reaction, obtain epoxychloropropane slurries, after membrane separator separates, obtain
Epoxychloropropane clear solution, then through subtractive processes such as desolventizing, de- light component, de- heavy constituents, obtain product epoxychloropropane.But
It is that this method equally can not achieve catalyst on-line regeneration and recycle.
To sum up, it would be highly desirable to find a kind of structure is simple, catalyst can on-line regeneration, it is at low cost, be suitable for industrialized production
The synthesis of epoxychloropropane and the device of catalyst on-line regeneration and chloropropene high conversion rate and to product selectivity height, urge
The long service life of agent, use cost is low, and reaction condition is mild, and wastewater discharge is less, and waste water COD is low, without intractable
Calcium chloride solid generates, the method for the synthesis and catalyst on-line regeneration of environmentally protective epoxychloropropane.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide a kind of structure letter
It is single, catalyst can on-line regeneration, the long service life of catalyst is at low cost, is suitable for the epoxychloropropane of industrialized production
The device of synthesis and catalyst on-line regeneration.
The further technical problems to be solved of the present invention are to overcome drawbacks described above of the existing technology, provide a kind of chlorine
Propylene conversion and to product selectivity height, the long service life of catalyst, use cost is low, and reaction condition is mild, waste water row
High-volume less, waste water COD is low, and no intractable calcium chloride solid generates, the synthesis and catalysis of environmentally protective epoxychloropropane
The method of agent on-line regeneration.
The technical solution adopted by the present invention to solve the technical problems is as follows: the synthesis of epoxychloropropane and catalyst are online
Regenerated device, including reaction kettle, N set wash kettle and regeneration kettle, N >=2；
The reaction kettle top is equipped with feed inlet, and lower part is equipped with discharge port, and discharge port is connect by circulating pump with valve, valve point
It is not connect with cooler and reaction kettle membrane filter, cooler is connected with the feed inlet of reaction kettle, and reaction kettle membrane filter is urged
Agent dope discharge port by valve respectively with the feed inlet of reaction kettle and set on first set wash the catalyst dope on kettle top into
Material mouth connection, the reaction kettle membrane filter clear liquid side are equipped with mixing clear liquid discharge port and backwash liquid charging containing epoxychloropropane
Mouthful；
1st set is washed kettle lower part equipped with discharge port, and discharge port is washed kettle membrane filter with the 1st set by circulating pump and connect, and the 1st set is washed kettle
The catalyst dope discharge port of membrane filter respectively be set to the 1st set and wash the catalyst concentrate circulating feed inlet on kettle top and be set to
The 2nd set of catalyst dope feed inlet for washing kettle top connects, and washes kettle membrane filter clear liquid side for described 1st set and is equipped with containing epoxy chloropropionate
The mixing clear liquid discharge port and backwash liquid feed inlet of alkane；
And so on；
N set washes kettle top equipped with fresh solvent feed inlet, and lower part is equipped with discharge port, and discharge port is washed by circulating pump and N set
The connection of kettle membrane filter, the catalyst dope discharge port that N set washes kettle membrane filter wash urging for kettle top with set on N set respectively
Agent concentrate circulating feed inlet is connected with the catalyst dope feed inlet set on regeneration kettle top, and N set is washed on kettle membrane filter
The circulation solvent clear liquid discharge port being equipped with is connect with the circulation solvent clear liquid feed inlet for washing kettle top set on N-1 set, the N
Set washes kettle membrane filter clear liquid side equipped with backwash liquid feed inlet；
The discharge port of the regeneration kettle lower part is connect with the regenerated catalyst dope feed inlet for being set to reaction kettle top；The regeneration
Pipeline between kettle and reaction kettle is equipped with decaying catalyst and unloads outlet.
The course of work of apparatus of the present invention are as follows: chloropropene, hydrogen peroxide, fresh solvent and catalyst are added instead by feed inlet
It answers kettle, and adjusts the pH value of reaction system with gas ammonia, carry out synthetic reaction, in reaction process, part reaction mass is from discharge port
After entering cooler cooling by circulating pump and valve, feed inlet is returned；After stable reaction, by valve, epoxy chloropropionate will be contained
The catalyst dope of alkane is sent into filtering and backwash in reaction kettle membrane filter, will the most of catalysis of filtering gained by valve
Agent dope returns to reaction kettle, and remaining fraction catalyst dope is sent into the 1st set and is washed in kettle, the mixing clear liquid containing epoxychloropropane by
Mixing clear liquid discharge port discharge containing epoxychloropropane；
The catalyst dope of reaction kettle membrane filter is before the 1st set of feeding is washed kettle, first by fresh solvent by fresh solvent feed inlet
It is sent into N set to wash in kettle, and washes kettle circulation to the 1st set step by step；
The catalyst dope being sent by reaction kettle membrane filter and the 2nd set wash the circulation solvent clear liquid of kettle return, wash kettle at the 1st set
After middle mixing, the 1st set is pumped by circulation and washes filtering and backwash in kettle membrane filter, it will the most of catalyst of filtering gained
Dope returns to the 1st set and washes kettle, and remaining fraction catalyst dope is sent into the 2nd set and is washed in kettle, the mixing clear liquid containing epoxychloropropane
By the mixing clear liquid discharge port discharge containing epoxychloropropane；
And so on；
It kettle membrane filter is washed by N-1 set is sent into N set and wash catalyst dope in kettle, and be added by fresh solvent feed inlet
After fresh solvent mixing, N set is pumped by circulation and washes filtering and backwash in kettle membrane filter, filtering gained circulation is molten
Agent clear liquid returns to N-1 set and washes kettle, and most of catalyst dope is returned to N set and washes kettle, remaining fraction catalyst dope
It is sent into regeneration kettle；
N set washes the catalyst dope of kettle membrane filter feeding in regeneration kettle, after carrying out regenerative response, regenerated catalyst dope
It is discharged by discharge port, and returns to reaction kettle through regenerated catalyst dope feed inlet.
After running a period of time, outlet is unloaded from decaying catalyst and draws off partial catalyst, and is mended from the feed inlet of reaction kettle
Enter considerable amount of fresh catalyst.
Preferably, steam heating jacket is enclosed with outside the reaction kettle and regeneration kettle.
Preferably, the reaction kettle, wash kettle and regeneration kettle in be equipped with agitating device.
It is as follows that the present invention further solves technical solution used by its technical problem: the synthesis and catalysis of epoxychloropropane
The method of agent on-line regeneration, comprising the following steps:
(1) synthesis of epoxychloropropane: chloropropene, hydrogen peroxide, fresh solvent and catalyst are added in reaction kettle, synthesized
It reacts, adjusts reaction system pH value with gas ammonia in reaction process and be maintained at neutral, obtain the catalyst dope containing epoxychloropropane, send
Enter and filter and backwash in reaction kettle membrane filter, obtains mixing clear liquid and catalyst dope containing epoxychloropropane, it will be most of
Catalyst dope returns to reaction kettle, and remaining fraction catalyst dope is sent into the 1st set and is washed in kettle；
(2) on-line cleaning of catalyst:
Fresh solvent is first sent into N set and washed in kettle by the catalyst dope of reaction kettle membrane filter before the 1st set of feeding is washed kettle,
And kettle circulation is washed to the 1st set step by step；
The catalyst dope being sent by reaction kettle membrane filter and the 2nd set wash the circulation solvent clear liquid of kettle return, wash kettle at the 1st set
After middle mixing, it is sent into the 1st set and washes filtering in kettle membrane filter and backwash, obtain epoxychloropropane mixing clear liquid and catalyst is dense
Liquid washes kettle for the 1st set of the return of most of catalyst dope, and remaining fraction catalyst dope is sent into the 2nd set and is washed in kettle；
And so on；
It washes kettle membrane filter by N-1 set to be sent into after the catalyst dope washed in kettle of N set mixes with fresh solvent, feeding N
Set, which is washed in kettle membrane filter, to be filtered and backwashes, and solvent clear liquid and catalyst dope must recycles, will circulation solvent clear liquid return the
N-1 set washes kettle, and most of catalyst dope is returned to N set and washes kettle, and remaining fraction catalyst dope is sent into regeneration kettle；
(3) regeneration of catalyst: N set washes the catalyst dope of kettle membrane filter feeding in regeneration kettle, carries out regenerative response
Afterwards, regenerated catalyst dope is returned into reaction kettle.
Preferably, in step (1), the molar ratio of hydrogen peroxide and fresh solvent in the chloropropene, hydrogen peroxide is 0.9
~6.0:1:3~4.The equation of chloropropene and hydroperoxidation are as follows: CH2ClCH=CH2 + H2O2→CH2ClCH-CH2(O)
+ H2O + Q.The mass fraction of hydrogen peroxide used in the method for the present invention is 27~50%.If the dosage of chloropropene is too low, chlorine
Propylene conversion is low, if the dosage of chloropropene is excessively high, chloropropene internal circulating load is big, and energy consumption is high.If the dosage of fresh solvent is too low,
Then grease compatibility is bad, influences the activity and selectivity of catalyst, if the dosage of fresh solvent is excessively high, solvent internal circulating load
Greatly, energy consumption is high.The method of the present invention can adjust charging equivalent under the ratio according to equipment capacity.
Preferably, in step (1), mass concentration of the catalyst in mixed system is 3~10%.If catalyst
Excessive concentration can then aggravate the load of membrane filter, and membrane filter flux is low, if the concentration of catalyst is too low, catalyst
Activity is low, selectivity is low.
Preferably, in step (1), the fresh solvent is one or more of methanol, ethyl alcohol, acetone or acetonitrile etc..
Preferably, in step (1), the catalyst is Titanium Sieve Molecular Sieve.
Preferably, the average grain diameter of the Titanium Sieve Molecular Sieve is 0.1~0.3 μm.
Preferably, in step (1), the temperature of the synthetic reaction is 40~120 DEG C, and pressure is 0.2~0.8MPa, time
For 0.5~6.0h.
Preferably, in step (1), the neutrality refers to that pH value is 6~7.
Preferably, in step (1), return to reaction kettle and be sent into the volume ratio for the catalyst dope that the 1st set is washed kettle for 90~
99:1~10.If a large amount of high activated catalysts, which enter, washes kettle, energy consumption is high, if small into the catalyst ratio for washing kettle, regenerates
Catalytic amount is small, and the activity of catalyst reactor is low, selectivity is low.
Preferably, in step (2), it is dense that the dosage of the fresh solvent is equivalent to plan the 1st set of catalyst for washing kettle of feeding
0.5~3.0 times (more preferable 0.6~2.0 times) of liquid product.If the amount of the fresh solvent for circulation is very few, in catalyst
The impurity displacement such as epoxychloropropane it is unclean, regeneration effect is poor, if the amount of circulation solvent clear liquid is excessive, solvent internal circulating load
Greatly, energy consumption is high.
Preferably, in step (2), returning to the volume ratio that the 1st set is washed the 2nd set of catalyst dope for washing kettle of kettle and feeding is
99.0~99.9:0.1~1.0.If being sent into, the 2nd set of amount for washing kettle is big, and regeneration catalyzing dosage is big, and energy consumption is high, if being sent into the 2nd set
The amount for washing kettle is small, then regeneration catalyzing dosage is small, and catalyst reactor activity is low, selectivity is low, cannot maintain line balancing.
Preferably, in step (2), returning to N set and washing kettle and be sent into the volume ratio of the catalyst dope of regeneration kettle is 99.0
~99.9:0.1~1.0.If the catalyst dope amount for being sent into regeneration kettle is excessive, energy consumption is high, if being sent into the catalyst of regeneration kettle
Dope amount is too small, then regenerated catalyst dosage cannot be guaranteed, to influence the activity and selectivity of catalyst reactor.
Preferably, step (1), in (2), the transmembrane pressure of the filtering≤the more preferable 50~150kPa of 200kPa(),
It filters to the concentration of catalyst to be concentrated into and is equivalent to catalyst 3~5 times of mass concentration in mixed system.If filtration pressure difference mistake
Height, then filter cake is thick, and flux is also low.
Preferably, step (1), in (2), the recoil pressure difference of the backwash≤500kPa.If the pressure difference that recoils is excessively high,
It will affect intensity and the service life of membrane tube, while energy consumption is high.
Preferably, in step (3), the temperature of the regenerative response is 120~280 DEG C, and pressure is 2~7MPa, and the time is
20~100h.The regeneration principle of the method for the present invention is impregnated with high-temperature solvent into catalyst, so that the impurity in catalyst is molten
Solution comes out.If the temperature or hypotony of regenerative response, impurity dissolution is incomplete, if the temperature of regenerative response or pressure mistake
Height, then energy consumption is high.
Preferably, in step (3), after driving, when one of conversion ratio of chloropropene or hydrogen peroxide or selectivity≤95%(more
Preferably 90~95%) when, the partial catalyst for regenerating kettle return reaction kettle is drawn off, and add fresh catalyst in step (1)
Agent.
Preferably, the discharged amount of the catalyst is equivalent to 2~8%(more preferable 4 of the catalyst quality of step (1) addition
~6%).
Preferably, the fresh catalyst added, which is equivalent to, draws off 1~2 times of catalyst quality.
The present invention is by driving process, being timed sample detection to the mixing clear liquid containing epoxychloropropane, obtaining
The conversion ratio and selective data (i.e. the activity and selectivity data of catalyst) of chloropropene and hydrogen peroxide in reaction kettle.
Beneficial effects of the present invention are as follows:
(1) apparatus of the present invention structure is simple, catalyst can on-line regeneration, the long service life of catalyst is at low cost, is suitable for work
Industry metaplasia produces；
(2) advantage of the method for the present invention is as follows:
1) conversion ratio >=99.5% of chloropropene, selectivity >=94.5%, conversion ratio >=99.5% of hydrogen peroxide, selectivity >=
95.0%；Not parking continuous production is after three months, conversion ratio >=90.0%, selectivity >=93.0% of chloropropene, the conversion of hydrogen peroxide
Rate >=99.5%, selectivity >=94.0%；After driving, when one of conversion ratio of chloropropene or hydrogen peroxide or selectivity≤95%, unload
Partial inactivation catalyst out, and comparable fresh catalyst is supplemented, after operation three months, conversion ratio >=99.5% of chloropropene, choosing
Selecting property >=94.0%, conversion ratio >=99.5% of hydrogen peroxide, selectivity >=95.0%, be basically stable at fresh catalyst activity and
Selectivity is horizontal；
2) long service life of catalyst is washed and is regenerated online by catalyst, and the activity and selectivity of catalyst is still reachable
90% or more of fresh catalyst, use cost is low；
3) reaction condition is mild；
4) wastewater discharge is less, about the 3~4% of chlorohydrination, and waste water COD is low (< 800ppm), meets national direct emission and refers to
Mark does not use lime in the treatment of waste water, and no intractable calcium chloride solid generates, environmentally protective.
Detailed description of the invention
Fig. 1 is the signal of the synthesis of the epoxychloropropane of the embodiment of the present invention 1~3 and the device of catalyst on-line regeneration
Figure.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
The mass fraction of hydrogen peroxide used in the embodiment of the present invention is 27.5% or 50%；Used in the embodiment of the present invention
Titanium Sieve Molecular Sieve, model TS-1 are purchased from Nanjing Xian Feng Nono-material Science & Technology Ltd., and average grain diameter is 0.2 μm；The present invention
Raw material or chemical reagent used in embodiment are obtained by routine business approach unless otherwise specified.
The embodiment of the present invention is by driving process, being timed sampling inspection to the mixing clear liquid containing epoxychloropropane
It surveys, obtains conversion ratio and selective data (the i.e. activity and selectivity number of catalyst of chloropropene and hydrogen peroxide in reaction kettle
According to).
The synthesis of epoxychloropropane and the Installation practice 1~3 of catalyst on-line regeneration
As shown in Figure 1, described device includes reaction kettle 1,1# washes kettle 2,2# washes kettle 3 and regeneration kettle 4；
1 top of reaction kettle is equipped with feed inlet 1-1, and lower part is equipped with discharge port 1-2, and discharge port 1-2 passes through circulating pump 1-3 and valve
Door 1-4-1 connection, valve 1-4-1 are connect with cooler 1-5 and reaction kettle membrane filter 1-6 respectively, cooler 1-5 and reaction kettle
1 feed inlet 1-1 connection, the catalyst dope discharge port 1-6-1 of reaction kettle membrane filter 1-6 by valve 1-4-2 respectively with
The feed inlet 1-1 of reaction kettle 1 is connected with the catalyst dope feed inlet 2-1 for washing 2 top of kettle set on 1#, the reaction kettle film filtering
Device 1-6 clear liquid side is equipped with mixing clear liquid discharge port 1-6-2 and backwash liquid feed inlet 1-6-3 containing epoxychloropropane；
The 1# washes 2 lower part of kettle and washes kettle membrane filter 2-4 company by circulating pump 2-3 and 1# equipped with discharge port 2-2, discharge port 2-2
Connect, 1# wash the catalyst dope discharge port 2-4-1 of kettle membrane filter 2-4 respectively with the catalyst dope that is set to 1# and washes 2 top of kettle
Recycle feed mouth 2-5 is connected with the catalyst dope feed inlet 3-6 for washing 3 top of kettle set on 2#, and the 1# washes kettle membrane filter 2-4
Clear liquid side is equipped with mixing clear liquid discharge port 2-4-2 and backwash liquid feed inlet 2-4-3 containing epoxychloropropane；
The 2# washes 3 top of kettle equipped with fresh solvent feed inlet 3-1, and lower part is equipped with discharge port 3-2, and discharge port 3-2 passes through circulation
Pump 3-3 and with 2# wash kettle membrane filter and connect 3-4 and connect, 2# wash the catalyst dope discharge port 3-4-1 of kettle membrane filter 3-4 respectively with
The catalyst concentrate circulating feed inlet 3-5 on 3 top of kettle is washed set on 2# and set on the catalyst dope feed inlet 4- for regenerating 4 top of kettle
1 connection, 2# wash the circulation solvent clear liquid discharge port 3-4-2 that kettle membrane filter 3-4 is equipped with and the circulation that 2 top of kettle is washed set on 1#
Solvent clear liquid feed inlet 2-6 connection, the 2# wash kettle membrane filter 3-4 clear liquid side equipped with backwash liquid feed inlet 3-4-3；
The discharge port 4-2 of regeneration 4 lower part of kettle is connect with the regenerated catalyst dope feed inlet 1-7 for being set to 1 top of reaction kettle；
Pipeline between the regeneration kettle 4 and reaction kettle 1 is equipped with decaying catalyst and unloads outlet 4-3；
The outside of the reaction kettle 1 and regeneration kettle 4 is enclosed with steam heating jacket 1-8,4-4 respectively；The reaction kettle 1,1# are washed
Kettle 2,2# are washed in kettle 3 and regeneration kettle 4 and are respectively equipped with agitating device 1-9,2-7,3-7,4-5.
The technical process of apparatus of the present invention are as follows: add chloropropene, hydrogen peroxide, fresh solvent and catalyst by feed inlet 1-1
Enter reaction kettle 1, and adjust the pH value of reaction system with gas ammonia, carry out synthetic reaction, in reaction process, part reaction mass is from going out
After material mouth 1-2 enters cooler 1-5 cooling by circulating pump 1-3 and valve 1-4-1, feed inlet 1-1 is returned；After stable reaction,
By valve 1-4-1, the catalyst dope containing epoxychloropropane is sent into reaction kettle membrane filter 1-6 and filters and backwashes,
By valve 1-4-2, the most of catalyst dope of filtering gained is returned into reaction kettle 1, remaining fraction catalyst dope is sent into
1# is washed in kettle 2, and the mixing clear liquid containing epoxychloropropane is discharged by the mixing clear liquid discharge port 1-6-2 containing epoxychloropropane；
The catalyst dope of reaction kettle membrane filter 1-6 is before being sent into 1# and washing kettle 2, first by fresh solvent by fresh solvent feed inlet
3-1 is sent into 2# and washes in kettle 3, and washes kettle 2 to 1# and recycle；
The circulation solvent clear liquid that kettle 3 returns is washed by the reaction kettle membrane filter 1-6 catalyst dope being sent into and 2#, washes kettle 2 in 1#
After middle mixing, 1# is sent by circulating pump 2-3 and washes filtering and backwash in kettle membrane filter 2-4, filtering gained is largely urged
Agent dope returns to 1# and washes kettle 2, and remaining fraction catalyst dope is sent into 2# and is washed in kettle 3, the mixing clear liquid containing epoxychloropropane
By the mixing clear liquid discharge port 2-4-2 discharge containing epoxychloropropane；
And so on；
It kettle membrane filter 2-4 is washed by 1# is sent into 2# and wash catalyst dope in kettle 3, and be added by fresh solvent feed inlet 3-1
After fresh solvent mixing, 2# is sent by circulating pump 3-3 and washes filtering and backwash in kettle membrane filter 3-4, filtering gained is followed
Ring solvent clear liquid returns to 1# and washes kettle 2, and most of catalyst dope return 2# is washed kettle 3, and remaining fraction catalyst dope is sent
Enter to regenerate in kettle 4；
2# washes the catalyst dope of kettle membrane filter 3-4 feeding in regeneration kettle 4, and after carrying out regenerative response, regenerated catalyst is dense
Liquid is discharged by discharge port 4-2, and returns to reaction kettle 1 through regenerated catalyst dope feed inlet 1-7.
After running a period of time, outlet 4-3 is unloaded from decaying catalyst and draws off partial catalyst, and from the charging of reaction kettle 1
Mouth 1-1 fills into considerable amount of fresh catalyst.
The synthesis of epoxychloropropane and the embodiment of the method 1 of catalyst on-line regeneration
(1) synthesis of epoxychloropropane: by chloropropene, hydrogen peroxide, methanol and Titanium Sieve Molecular Sieve respectively with 7.27t/h(95kmol/
H), 12.37t/h(27.5wt%, 100kmol/h), 9.61t/h(300kmol/h), the mass concentration that is equivalent in mixed system
3%(catalyst gross mass is 2.1t), it is added in reaction kettle 1, at 120 DEG C, 0.4MPa, carries out synthetic reaction 0.5h, reacted
Cheng Zhongyong gas ammonia adjusts reaction system pH value and is maintained at 7, obtains the catalyst dope containing epoxychloropropane, is sent into the filtering of reaction kettle film
In device 1-6, in the case where transmembrane pressure is 50~150kPa, filters to the concentration of catalyst and be concentrated into 15%, then kickback pressure≤
It under 500kPa, is backwashed, obtains mixing clear liquid and catalyst dope containing epoxychloropropane, it will wherein percentage by volume 99%
Catalyst dope return to reaction kettle 1, the catalyst dope of percentage by volume 1% is sent into 1# and is washed in kettle 2；
(2) on-line cleaning of catalyst:
The catalyst dope of reaction kettle membrane filter 1-6 first will be equivalent to plan feeding 1# and wash kettle 2 before being sent into 1# and washing kettle 2
The fresh solvent methanol of 1.0 times of catalyst dope volume is sent into 2# and is washed in kettle 3, and washes kettle 2 to 1# and recycle；
It is washed the circulation solvent clear liquid that kettle 3 returns by the reaction kettle membrane filter 1-6 catalyst dope being sent into and 2# and is washed in kettle 2 in 1#
It after mixing, is sent into 1# and washes in kettle membrane filter 2-4, in the case where transmembrane pressure is 50~150kPa, the concentration of filtering to catalyst is dense
It is reduced to 15%, then at kickback pressure≤500kPa, is backwashed, epoxychloropropane mixing clear liquid and catalyst dope are obtained, it will
The catalyst dope of percentage by volume 99.9% returns to 1# and washes kettle 2, and the catalyst dope of percentage by volume 0.1% is sent into 2# and washes kettle 3
In；
And so on；
It washes kettle membrane filter 2-4 by 1# to be sent into after the catalyst dope washed in kettle 3 of 2# mixes with fresh solvent methanol, feeding 2# is washed
In kettle membrane filter 3-4, in the case where transmembrane pressure is 50~150kPa, filters to the concentration of catalyst and be concentrated into 15%, then recoiling
It under pressure≤500kPa, is backwashed, solvent clear liquid and catalyst dope must be recycled, circulation solvent clear liquid is returned into 1# and washes kettle
2, and the catalyst dope of percentage by volume 99.8% return 2# is washed into kettle, the catalyst dope of percentage by volume 0.2% is sent into again
In raw kettle 4；
(3) regeneration of catalyst: 2# wash kettle membrane filter 3-4 feeding catalyst dope regeneration kettle 4 in, 120 DEG C,
Under 2.0MPa, after carrying out regenerative response 20h, regenerated catalyst dope is returned into reaction kettle 1.
Through detecting, in the mixing clear liquid containing epoxychloropropane, the conversion ratio of chloropropene is 99.5%, selectivity is 96.5%；
The conversion ratio of hydrogen peroxide is 99.5%, selectivity is 95.0%.
Not parking continuous production is after three months, through detecting, in the mixing clear liquid containing epoxychloropropane, and the conversion ratio of chloropropene
It is 93.0% for 97.0%, selectivity, the conversion ratio of hydrogen peroxide is 99.5%, selectivity is 94.0%.
Drive one month and two after half a month (selectivity of chloropropene is minimum, respectively 94.5%, 95.0%), draw off respectively
100kg decaying catalyst, and 150kg fresh catalyst is supplemented, it is mixed containing epoxychloropropane through detecting after running three months altogether
It closes in clear liquid, the conversion ratio of chloropropene is 99.5%, selectivity is 96.5%, and the conversion ratio of hydrogen peroxide is 99.5%, selectivity is
95.0%。
The synthesis of epoxychloropropane and the embodiment of the method 2 of catalyst on-line regeneration
(1) synthesis of epoxychloropropane: by chloropropene, hydrogen peroxide, ethyl alcohol and Titanium Sieve Molecular Sieve respectively with 22.96t/h
(300kmol/h), 10.20t/h(50wt%, 150kmol/h), 27.64t/h(600kmol/h), be equivalent in mixed system
Mass concentration 10%(catalyst gross mass is 7t), it is added in reaction kettle 1, at 40 DEG C, 0.2MPa, carries out synthetic reaction 6.0h,
Adjusting reaction system pH value with gas ammonia in reaction process is 7, obtains the catalyst dope containing epoxychloropropane, is sent into reaction kettle film mistake
In filter 1-6, in the case where transmembrane pressure is 50~150kPa, filters to the concentration of catalyst and be concentrated into 30%, then kickback pressure≤
It under 500kPa, is backwashed, obtains mixing clear liquid and catalyst dope containing epoxychloropropane, it will wherein percentage by volume 90%
Catalyst dope return to reaction kettle 1, the catalyst dope of percentage by volume 10% is sent into 1# and is washed in kettle 2；
(2) on-line cleaning of catalyst:
The catalyst dope of reaction kettle membrane filter 1-6 first will be equivalent to plan feeding 1# and wash kettle 2 before being sent into 1# and washing kettle 2
The fresh solvent ethyl alcohol of 1.5 times of catalyst dope volume is sent into 2# and is washed in kettle 3, and washes kettle 2 to 1# and recycle；
It is washed the circulation solvent clear liquid that kettle 3 returns by the reaction kettle membrane filter 1-6 catalyst dope being sent into and 2# and is washed in kettle 2 in 1#
It after mixing, is sent into 1# and washes in kettle membrane filter 2-4, in the case where transmembrane pressure is 50~150kPa, the concentration of filtering to catalyst is dense
It is reduced to 30%, then at kickback pressure≤500kPa, is backwashed, epoxychloropropane mixing clear liquid and catalyst dope are obtained, it will
The catalyst dope of percentage by volume 99.0% returns to 1# and washes kettle 2, and the catalyst dope of percentage by volume 1.0% is sent into 2# and washes kettle 3
In；
And so on；
It washes kettle membrane filter 2-4 by 1# to be sent into after the catalyst dope washed in kettle 3 of 2# mixes with fresh solvent ethyl alcohol, feeding 2# is washed
In kettle membrane filter 3-4, in the case where transmembrane pressure is 50~150kPa, filters to the concentration of catalyst and be concentrated into 30%, then recoiling
It under pressure≤500kPa, is backwashed, solvent clear liquid and catalyst dope must be recycled, circulation solvent clear liquid is returned into 1# and washes kettle
2, and the catalyst dope of percentage by volume 99.7% return 2# is washed into kettle, the catalyst dope of percentage by volume 0.3% is sent into again
In raw kettle 4；
(3) regeneration of catalyst: 2# wash kettle membrane filter 3-4 feeding catalyst dope regeneration kettle 4 in, 280 DEG C,
Under 7.0MPa, after carrying out regenerative response 100h, regenerated catalyst dope is returned into reaction kettle 1.
Through detecting, in the mixing clear liquid containing epoxychloropropane, the conversion ratio of chloropropene is 99.5%, selectivity is 95.5%；
The conversion ratio of hydrogen peroxide is 99.5%, selectivity is 97.0%.
Not parking continuous production is after three months, through detecting, in the mixing clear liquid containing epoxychloropropane, and the conversion ratio of chloropropene
It is 93.0% for 91.0%, selectivity, the conversion ratio of hydrogen peroxide is 99.5%, selectivity is 94.0%.
Driving after two months, (conversion ratio of chloropropene is minimum, 93.0%), to draw off 300kg decaying catalyst, and supplement
300kg fresh catalyst, after operation three months, through detecting, in the mixing clear liquid containing epoxychloropropane, the conversion ratio of chloropropene is
99.5%, selectivity is 95.0%, and the conversion ratio of hydrogen peroxide is 99.5%, selectivity is 95.0%.
The synthesis of epoxychloropropane and the embodiment of the method 3 of catalyst on-line regeneration
(1) synthesis of epoxychloropropane: by chloropropene, hydrogen peroxide, acetonitrile and methanol quality than the mixture and titanium silicon point for 1:1
Son screening not with 36.73t/h(480kmol/h), 9.90t/h(27.5wt%, 80kmol/h), 11.52t/h(320kmol/h),
The mass concentration 5%(catalyst gross mass being equivalent in mixed system is 3.5t), it is added in reaction kettle 1, in 60 DEG C, 0.8MPa
Under, synthetic reaction 3.0h is carried out, adjusting reaction system pH value with gas ammonia in reaction process is 7, obtains the catalysis containing epoxychloropropane
Agent dope is sent into reaction kettle membrane filter 1-6, and in the case where transmembrane pressure is 50~150kPa, the concentration of filtering to catalyst is dense
It is reduced to 25%, then at kickback pressure≤500kPa, is backwashed, mixing clear liquid containing epoxychloropropane is obtained and catalyst is dense
The catalyst dope of wherein percentage by volume 95% is returned to reaction kettle 1 by liquid, and the catalyst dope of percentage by volume 5% is sent into 1#
It washes in kettle 2；
(2) on-line cleaning of catalyst:
The catalyst dope of reaction kettle membrane filter 1-6 first will be equivalent to plan feeding 1# and wash kettle 2 before being sent into 1# and washing kettle 2
The fresh solvent (acetonitrile and methanol quality are than mixture for 1:1) of 0.6 times of catalyst dope volume is sent into 2# and is washed in kettle 3, and
Kettle 2 is washed to 1# to recycle；
It is washed the circulation solvent clear liquid that kettle 3 returns by the reaction kettle membrane filter 1-6 catalyst dope being sent into and 2# and is washed in kettle 2 in 1#
It after mixing, is sent into 1# and washes in kettle membrane filter 2-4, in the case where transmembrane pressure is 50~150kPa, the concentration of filtering to catalyst is dense
It is reduced to 25%, then at kickback pressure≤500kPa, is backwashed, epoxychloropropane mixing clear liquid and catalyst dope are obtained, it will
The catalyst dope of percentage by volume 99.5% returns to 1# and washes kettle 2, and the catalyst dope of percentage by volume 0.5% is sent into 2# and washes kettle 3
In；
And so on；
Kettle membrane filter 2-4 is washed by 1# to be sent into the catalyst dope washed in kettle 3 of 2# and fresh solvent (acetonitrile is with methanol quality ratio
The mixture of 1:1) after mixing, it is sent into 2# and washes in kettle membrane filter 3-4, in the case where transmembrane pressure is 50~150kPa, filtering is to urging
The concentration of agent is concentrated into 25%, then at kickback pressure≤500kPa, is backwashed, and solvent clear liquid and catalyst must be recycled
Circulation solvent clear liquid is returned to 1# and washes kettle 2, and the catalyst dope of percentage by volume 99.9% return 2# is washed kettle, volume by dope
The catalyst dope of percentage 0.1% is sent into regeneration kettle 4；
(3) regeneration of catalyst: 2# wash kettle membrane filter 3-4 feeding catalyst dope regeneration kettle 4 in, 170 DEG C,
Under 3.5MPa, after carrying out regenerative response 40h, regenerated catalyst dope is returned into reaction kettle 1.
Through detecting, in the mixing clear liquid containing epoxychloropropane, the conversion ratio of chloropropene is 99.5%, selectivity is 94.5%；
The conversion ratio of hydrogen peroxide is 99.5%, selectivity is 96.0%.
Not parking continuous production is after three months, through detecting, in the mixing clear liquid containing epoxychloropropane, and the conversion ratio of chloropropene
It is 94.0% for 90.0%, selectivity, the conversion ratio of hydrogen peroxide is 99.5%, selectivity is 94.0%.
(conversion ratio of chloropropene is minimum, 95.0%), to draw off 200kg decaying catalyst, and supplement after driving one and a half months
400kg fresh catalyst, after operation three months, through detecting, in the mixing clear liquid containing epoxychloropropane, the conversion ratio of chloropropene is
99.5%, selectivity is 94.0%, and the conversion ratio of hydrogen peroxide is 99.5%, selectivity is 95.0%.
Claims (10)
1. a kind of synthesis of epoxychloropropane and the device of catalyst on-line regeneration, it is characterised in that: washed including reaction kettle, N set
Kettle and regeneration kettle, N >=2；
The reaction kettle top is equipped with feed inlet, and lower part is equipped with discharge port, and discharge port is connect by circulating pump with valve, valve point
It is not connect with cooler and reaction kettle membrane filter, cooler is connected with the feed inlet of reaction kettle, and reaction kettle membrane filter is urged
Agent dope discharge port by valve respectively with the feed inlet of reaction kettle and set on first set wash the catalyst dope on kettle top into
Material mouth connection, the reaction kettle membrane filter clear liquid side are equipped with mixing clear liquid discharge port and backwash liquid charging containing epoxychloropropane
Mouthful；
1st set is washed kettle lower part equipped with discharge port, and discharge port is washed kettle membrane filter with the 1st set by circulating pump and connect, and the 1st set is washed kettle
The catalyst dope discharge port of membrane filter respectively be set to the 1st set and wash the catalyst concentrate circulating feed inlet on kettle top and be set to
The 2nd set of catalyst dope feed inlet for washing kettle top connects, and washes kettle membrane filter clear liquid side for described 1st set and is equipped with containing epoxy chloropropionate
The mixing clear liquid discharge port and backwash liquid feed inlet of alkane；
And so on；
N set washes kettle top equipped with fresh solvent feed inlet, and lower part is equipped with discharge port, and discharge port is washed by circulating pump and N set
The connection of kettle membrane filter, the catalyst dope discharge port that N set washes kettle membrane filter wash urging for kettle top with set on N set respectively
Agent concentrate circulating feed inlet is connected with the catalyst dope feed inlet set on regeneration kettle top, and N set is washed on kettle membrane filter
The circulation solvent clear liquid discharge port being equipped with is connect with the circulation solvent clear liquid feed inlet for washing kettle top set on N-1 set, the N
Set washes kettle membrane filter clear liquid side equipped with backwash liquid feed inlet；
The discharge port of the regeneration kettle lower part is connect with the regenerated catalyst dope feed inlet for being set to reaction kettle top；The regeneration
Pipeline between kettle and reaction kettle is equipped with decaying catalyst and unloads outlet.
2. the device of the synthesis of epoxychloropropane and catalyst on-line regeneration according to claim 1, it is characterised in that: described
Steam heating jacket is enclosed with outside reaction kettle and regeneration kettle；The reaction kettle is washed in kettle and regeneration kettle to be equipped with and stirs dress
It sets.
3. the method for carrying out the synthesis and catalyst on-line regeneration of epoxychloropropane with device as claimed in claim 1 or 2, feature
It is, comprising the following steps:
(1) synthesis of epoxychloropropane: chloropropene, hydrogen peroxide, fresh solvent and catalyst are added in reaction kettle, synthesized
It reacts, adjusts reaction system pH value with gas ammonia in reaction process and be maintained at neutral, obtain the catalyst dope containing epoxychloropropane, send
Enter and filter and backwash in reaction kettle membrane filter, obtains mixing clear liquid and catalyst dope containing epoxychloropropane, it will be most of
Catalyst dope returns to reaction kettle, and remaining fraction catalyst dope is sent into the 1st set and is washed in kettle；
(2) on-line cleaning of catalyst:
Fresh solvent is first sent into N set and washed in kettle by the catalyst dope of reaction kettle membrane filter before the 1st set of feeding is washed kettle,
And kettle circulation is washed to the 1st set step by step；
The catalyst dope being sent by reaction kettle membrane filter and the 2nd set wash the circulation solvent clear liquid of kettle return, wash kettle at the 1st set
After middle mixing, it is sent into the 1st set and washes filtering in kettle membrane filter and backwash, obtain epoxychloropropane mixing clear liquid and catalyst is dense
Liquid washes kettle for the 1st set of the return of most of catalyst dope, and remaining fraction catalyst dope is sent into the 2nd set and is washed in kettle；
And so on；
It washes kettle membrane filter by N-1 set to be sent into after the catalyst dope washed in kettle of N set mixes with fresh solvent, feeding N
Set, which is washed in kettle membrane filter, to be filtered and backwashes, and solvent clear liquid and catalyst dope must recycles, will circulation solvent clear liquid return the
N-1 set washes kettle, and most of catalyst dope is returned to N set and washes kettle, and remaining fraction catalyst dope is sent into regeneration kettle；
(3) regeneration of catalyst: N set washes the catalyst dope of kettle membrane filter feeding in regeneration kettle, carries out regenerative response
Afterwards, regenerated catalyst dope is returned into reaction kettle.
4. the method for the synthesis of epoxychloropropane and catalyst on-line regeneration according to claim 3, it is characterised in that: step
(1) in, the molar ratio of hydrogen peroxide and fresh solvent in the chloropropene, hydrogen peroxide is 0.9~6.0:1:3~4；It is described to urge
Mass concentration of the agent in mixed system is 3~10%；The fresh solvent is one of methanol, ethyl alcohol, acetone or acetonitrile
Or it is several；The catalyst is Titanium Sieve Molecular Sieve；The average grain diameter of the Titanium Sieve Molecular Sieve is 0.1~0.3 μm.
5. according to the synthesis of the epoxychloropropane of claim 3 or 4 and the method for catalyst on-line regeneration, it is characterised in that:
In step (1), the temperature of the synthetic reaction is 40~120 DEG C, and pressure is 0.2~0.8MPa, and the time is 0.5~6.0h；It returns
Returning reaction kettle and being sent into the volume ratio for the catalyst dope that the 1st set is washed kettle is 90~99:1~10.
6. the method for the synthesis and catalyst on-line regeneration of the epoxychloropropane according to one of claim 3~5, feature exist
In: in step (2), the dosage of the fresh solvent be equivalent to plan be sent into the catalyst dope volume that the 1st set is washed kettle 0.5~
3.0 again；Returning to the 1st set and washing kettle and be sent into the volume ratio for the catalyst dope that the 2nd set is washed kettle is 99.0~99.9:0.1~1.0.
7. the method for the synthesis and catalyst on-line regeneration of the epoxychloropropane according to one of claim 3~6, feature exist
In: in step (2), return N set wash kettle and be sent into regeneration kettle catalyst dope volume ratio be 99.0~99.9:0.1~
1.0。
8. the method for the synthesis and catalyst on-line regeneration of the epoxychloropropane according to one of claim 3~7, feature exist
In: in step (1), (2), the transmembrane pressure of the filtering≤200kPa, filter to the concentration of catalyst to be concentrated into and be equivalent to
Catalyst is 3~5 times of mass concentration in mixed system；The recoil pressure difference of the backwash≤500kPa.
9. the method for the synthesis and catalyst on-line regeneration of the epoxychloropropane according to one of claim 3~8, feature exist
In: in step (3), the temperature of the regenerative response is 120~280 DEG C, and pressure is 2~7MPa, and the time is 20~100h.
10. the method for the synthesis and catalyst on-line regeneration of the epoxychloropropane according to one of claim 3~9, feature
It is: in step (3), after driving, when one of conversion ratio of chloropropene or hydrogen peroxide or selectivity≤95%, regeneration kettle is returned
The partial catalyst for returning reaction kettle is drawn off, and adds fresh catalyst in step (1)；The discharged amount of the catalyst is equivalent to
The 2~8% of the catalyst quality that step (1) is added；The fresh catalyst added, which is equivalent to, draws off the 1~2 of catalyst quality
Times.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110479387A (en) * | 2019-09-02 | 2019-11-22 | 中国天辰工程有限公司 | One kind is for solid-phase catalyst cleaning and regeneration method in catalyst liquid-solid reaction system |
| WO2022155782A1 (en) * | 2021-01-19 | 2022-07-28 | 汇智工程科技股份有限公司 | Safety instrument system for graphite synthesis furnace and chlorination reactor in production of epichlorohydrin |
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|---|---|---|---|---|
| CN103055543A (en) * | 2012-12-29 | 2013-04-24 | 上海安赐机械设备有限公司 | Large-channel vertical-flow membrane device for recycling superfine solid catalyst and process |
| CN203379637U (en) * | 2012-12-29 | 2014-01-08 | 上海安赐机械设备有限公司 | Large-channel vertical membrane flowing device for recycling superfine solid catalysts |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055543A (en) * | 2012-12-29 | 2013-04-24 | 上海安赐机械设备有限公司 | Large-channel vertical-flow membrane device for recycling superfine solid catalyst and process |
| CN203379637U (en) * | 2012-12-29 | 2014-01-08 | 上海安赐机械设备有限公司 | Large-channel vertical membrane flowing device for recycling superfine solid catalysts |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479387A (en) * | 2019-09-02 | 2019-11-22 | 中国天辰工程有限公司 | One kind is for solid-phase catalyst cleaning and regeneration method in catalyst liquid-solid reaction system |
| WO2022155782A1 (en) * | 2021-01-19 | 2022-07-28 | 汇智工程科技股份有限公司 | Safety instrument system for graphite synthesis furnace and chlorination reactor in production of epichlorohydrin |
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