CN110003140B - Device and method for synthesizing epichlorohydrin and regenerating catalyst on line - Google Patents
Device and method for synthesizing epichlorohydrin and regenerating catalyst on line Download PDFInfo
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- CN110003140B CN110003140B CN201910343916.XA CN201910343916A CN110003140B CN 110003140 B CN110003140 B CN 110003140B CN 201910343916 A CN201910343916 A CN 201910343916A CN 110003140 B CN110003140 B CN 110003140B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 338
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 64
- 230000001172 regenerating effect Effects 0.000 title claims description 27
- 230000002194 synthesizing effect Effects 0.000 title claims description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 172
- 238000005406 washing Methods 0.000 claims abstract description 118
- 230000008929 regeneration Effects 0.000 claims abstract description 74
- 238000011069 regeneration method Methods 0.000 claims abstract description 74
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims abstract description 50
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000012141 concentrate Substances 0.000 claims description 116
- 239000012528 membrane Substances 0.000 claims description 83
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 79
- 239000002904 solvent Substances 0.000 claims description 71
- 239000007788 liquid Substances 0.000 claims description 63
- 238000001914 filtration Methods 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000011010 flushing procedure Methods 0.000 claims description 28
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 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 8
- 230000001502 supplementing effect Effects 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 239000002351 wastewater Substances 0.000 abstract description 11
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 4
- 239000001110 calcium chloride Substances 0.000 abstract description 4
- 229910001628 calcium chloride Inorganic materials 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 13
- 238000001514 detection method Methods 0.000 description 9
- 238000005265 energy consumption Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006735 epoxidation reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 5
- 238000010924 continuous production Methods 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000007789 gas Substances 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
- 239000002002 slurry Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 3
- MLHOXUWWKVQEJB-UHFFFAOYSA-N Propyleneglycol diacetate Chemical compound CC(=O)OC(C)COC(C)=O MLHOXUWWKVQEJB-UHFFFAOYSA-N 0.000 description 3
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 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
- 239000000006 Nitroglycerin Substances 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 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
- 229910021529 ammonia Inorganic materials 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
- 238000005266 casting Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 229960003711 glyceryl trinitrate Drugs 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- DOKHEARVIDLSFF-UHFFFAOYSA-N prop-1-en-1-ol Chemical group CC=CO DOKHEARVIDLSFF-UHFFFAOYSA-N 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000010865 sewage Substances 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
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002699 waste material Substances 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
Abstract
The device comprises a reaction kettle, an N set of washing kettles and a regeneration kettle, wherein N is more than or equal to 2. The method comprises the steps of synthesis of epichlorohydrin, on-line cleaning of a catalyst and regeneration of the catalyst. The device has simple structure, the catalyst can be regenerated on line, the service life of the catalyst is long, the cost is low, and the device is suitable for industrial production; the method has the advantages of high chloropropene conversion rate and selectivity to products, long service life of the catalyst, low use cost, mild reaction conditions, less wastewater discharge, low COD of wastewater, no production of calcium chloride solids which are difficult to treat, and environmental protection.
Description
Technical Field
The invention particularly relates to a device and a method for synthesizing epichlorohydrin and regenerating a catalyst on line.
Background
The epoxy chloropropane is an important organic chemical raw material and a fine chemical product, and has very wide application. The epoxy resin prepared by using the epoxy resin as a raw material has the characteristics of strong cohesiveness, chemical medium corrosion resistance, good chemical stability, high impact strength, excellent dielectric property and the like, and has wide application in industries such as coating, adhesive, reinforcing material, casting material, electronic laminate and the like. In addition, the epichlorohydrin can be used for synthesizing various products such as glycerol, nitroglycerin explosive, glass fiber reinforced plastic, electric insulation products, surfactants, medicines, pesticides, coatings, sizing materials, ion exchange resins, plasticizers, (condensed) water glycerol derivatives, chlorohydrin rubber and the like, and can be used as solvents of cellulose esters, resins and cellulose ethers, and used for producing chemical stabilizers, chemical dyes, water treatment agents and the like.
The production of epichlorohydrin began in the 30 s of the last century. In 1945, shell chemical company began industrialized production of chlorohydrin method (or allyl chloride method, chloropropene method); in 1955, the Dow chemical company became the world manufacturer of 2 nd domestic propylene high temperature chlorination process for producing epichlorohydrin; in 1985, japanese Showa electric company began to produce epichlorohydrin by the propylene acetate method (or allyl alcohol method), and industrialization of the method was realized in the same year; large-scale production equipment of glycerol-method epichlorohydrin, which is built and rapidly put into production by the Chinese chemical and Suwei declaration in 2006. Currently, the industrial epichlorohydrin production process mainly comprises the three methods, and the methods are specifically as follows.
(1) Propylene high temperature chlorination process:
advantages are: 1) The process is mature and the operation is stable; 2) The introduction cost is low, and the investment cost of the device is lower than that of the propylene acetate method; 3) The intermediate chloropropene can be used for producing pesticides, resins and the like. In actual production, the two products of chloropropene and epichlorohydrin can be regulated according to market conditions, and balanced production is realized.
Disadvantages: 1) The reaction byproducts are more, the conversion rate of raw materials is low, and the consumption ration is higher; 2) Equipment corrosion is serious, and energy consumption is high; 3) The sewage discharge amount is large.
(2) Propylene acetate process:
Advantages are: 1) The acetyl chlorination technology is adopted, so that the yield is high, and the raw material consumption is low; 2) The product quality is higher, the purity is high; 3) The high-temperature chlorination reaction is avoided, the reaction condition is mild, the operation is stable, the propylene consumption is reduced, and the consumption of Ca (OH) 2 and chlorine is almost reduced by half; 4) The discharge of reaction byproducts and CaCl 2 -containing wastewater is greatly reduced.
Disadvantages: 1) The reaction steps are more, the process route is long and complex, and a large amount of saponification wastewater still needs to be discharged; 2) Acetic acid is arranged in the system, and stainless steel equipment is needed; 3) The oxidation reactor is bulky, the catalyst is expensive and cannot be regenerated; 4) The safety and reliability of the propenol unit for preventing the explosion of the mixed gas must be very important when oxygen and recycle gas (including oxygen, propylene and the like) compressed gas are added in the reaction.
(3) Glycerol chlorination process:
advantages are: 1) The process flow is short, the reactor part does not need to operate in a high temperature state, and the investment is low; 2) The biodiesel byproduct glycerol is utilized, so that the cost of raw materials for production is relatively low; 3) Less by-products, low waste treatment cost, mild operation condition and safety.
Disadvantages: 1) The production time is short, and the experience is little; 2) Industrial glycerin is expensive and only byproduct glycerin can be used as a raw material.
CN101747297a discloses a process for continuously producing epichlorohydrin, which comprises introducing 3-chloropropene, hydrogen peroxide and a solvent into a plurality of fixed bed reactors containing titanium silicalite catalyst, and subjecting the 3-chloropropene and hydrogen peroxide to epoxidation reaction; the epoxidation reaction is stopped in at least one fixed bed reactor, and the catalyst therein is regenerated, wherein when the catalyst regeneration is performed in any one reactor, the epoxidation reaction is performed in at least one reactor among other reactors. Although the method simplifies the separation process of the catalyst and the reaction product, the long-period continuous stable operation of the epichlorohydrin production process can be realized, the loss caused by equipment shutdown is reduced, the process is simple, and the flow is convenient to realize. However, the catalyst used in the method is granular or columnar, has large particles, small specific surface area and low activity, and can not realize online regeneration and recycling of the catalyst because the catalyst is required to be overhauled and replaced by stopping a tower when the activity is reduced along with the prolonged service time and the regeneration effect is poor.
CN101486690a discloses a method for preparing ECH (epichlorohydrin) by epoxidation of chloropropene, which comprises the steps of putting chloropropene, solvent and titanium silicalite molecular sieve catalyst fine particles into a reaction kettle, and adding hydrogen peroxide at 10-80 ℃; the reaction is carried out under the weak acid condition, and the reacted materials are subjected to oil-water delamination by an intermediate tank and are divided into an oil phase and a water phase; sending the oil phase into a rectifying tower to separate chloropropene and ECH, filtering the water phase, washing a catalyst filter cake by a solvent, regenerating or directly pulping by the solvent, applying the catalyst filter cake to epoxidation, extracting ECH in the filtered water layer by chloropropene, and combining and rectifying an extracted oil layer with an oil layer obtained by separating a reaction liquid, or applying the extracted oil layer to epoxidation; the raffinate water is rectified to recycle methanol, and the methanol is used for preparing the catalyst. Although the method has simple flow, less solvent consumption, high separation yield of reaction products and easy industrialization, the method does not realize continuous production, and continuous online regeneration and recycling of the catalyst are not realized.
CN107033107a discloses a method for preparing epichlorohydrin, which is to add catalyst, pH regulator and solvent on the external circulation pipeline of slurry bed curing reactor, then mix the three components in the first-stage static mixer, then make chloropropene and hydrogen peroxide added in the pipeline reactor to make chloropropene epoxidation homogeneous catalytic reaction, then cool the reactor, mix the components in the second-stage static mixer, and make curing reaction in slurry bed curing reactor to obtain epichlorohydrin slurry, then separate the epichlorohydrin slurry by membrane separator to obtain epichlorohydrin clear solution, and then make refining processes of desolventizing, light component removing, recombination removing, etc. to obtain the product epichlorohydrin. But the method can not realize the online regeneration and recycling of the catalyst.
In summary, it is needed to find a device which has a simple structure, a catalyst capable of being regenerated on line, a low cost and suitable for the synthesis of epoxy chloropropane in industrial production and the on-line regeneration of the catalyst, and a method which has the advantages of high chloropropene conversion rate, high selectivity to products, long service life of the catalyst, low use cost, mild reaction condition, less wastewater discharge, low wastewater COD, no production of refractory calcium chloride solid, and environmental protection for the synthesis of epoxy chloropropane and the on-line regeneration of the catalyst.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects in the prior art and providing the device for synthesizing the epichlorohydrin and regenerating the catalyst on line, which has the advantages of simple structure, on-line regeneration of the catalyst, long service life of the catalyst and low cost and is suitable for industrial production.
The invention further solves the technical problems of the prior art, and provides a method for synthesizing the epoxy chloropropane and regenerating the catalyst on line, which has the advantages of high chloropropene conversion rate, high selectivity to products, long service life of the catalyst, low use cost, mild reaction condition, less wastewater discharge, low COD of wastewater, no production of refractory calcium chloride solid, and environmental protection.
The technical scheme adopted for solving the technical problems is as follows: the device for synthesizing epoxy chloropropane and regenerating the catalyst on line comprises a reaction kettle, an N set of washing kettles and a regeneration kettle, wherein N is more than or equal to 2;
the upper part of the reaction kettle is provided with a feed inlet, the lower part of the reaction kettle is provided with a discharge outlet, the discharge outlet is connected with a valve through a circulating pump, the valve is respectively connected with a cooler and a reaction kettle membrane filter, the cooler is connected with the feed inlet of the reaction kettle, a catalyst concentrate discharge outlet of the reaction kettle membrane filter is respectively connected with the feed inlet of the reaction kettle and a catalyst concentrate feed inlet arranged at the upper part of the first washing kettle through a valve, and the clear liquid side of the reaction kettle membrane filter is provided with a mixed clear liquid discharge outlet containing epichlorohydrin and a backflushing liquid feed inlet;
The lower part of the 1 st washing kettle is provided with a discharge hole, the discharge hole is connected with the 1 st washing kettle membrane filter through a circulating pump, the catalyst concentrate discharge hole of the 1 st washing kettle membrane filter is respectively connected with a catalyst concentrate circulating feed hole arranged at the upper part of the 1 st washing kettle and a catalyst concentrate feed hole arranged at the upper part of the 2 nd washing kettle, and the clear liquid side of the 1 st washing kettle membrane filter is provided with a mixed clear liquid discharge hole containing epichlorohydrin and a backflushing liquid feed hole;
And so on;
The upper part of the Nth set of washing kettle is provided with a fresh solvent feed inlet, the lower part of the Nth set of washing kettle is provided with a discharge port, the discharge port is connected with the Nth set of washing kettle membrane filter through a circulating pump, the catalyst concentrate discharge port of the Nth set of washing kettle membrane filter is respectively connected with a catalyst concentrate circulating feed inlet arranged at the upper part of the Nth set of washing kettle and a catalyst concentrate feed inlet arranged at the upper part of the regeneration kettle, the circulating solvent clear liquid discharge port arranged on the Nth set of washing kettle membrane filter is connected with a circulating solvent clear liquid feed inlet arranged at the upper part of the N-1 th set of washing kettle, and the clear liquid side of the Nth set of washing kettle membrane filter is provided with a recoil liquid feed inlet;
the discharge port at the lower part of the regeneration kettle is connected with the regenerated catalyst concentrated solution feed port at the upper part of the reaction kettle; and an inactive catalyst discharging outlet is arranged on a pipeline between the regeneration kettle and the reaction kettle.
The working process of the device of the invention is as follows: adding chloropropene, hydrogen peroxide, fresh solvent and catalyst into a reaction kettle from a feed port, regulating the pH value of a reaction system by using ammonia gas, and carrying out a synthetic reaction, wherein part of reaction materials enter a cooler from a discharge port through a circulating pump and a valve to be cooled in the reaction process, and then return to the feed port; after the reaction is stable, sending the catalyst concentrate containing the epoxy chloropropane into a reaction kettle membrane filter through a valve, filtering and back flushing, returning most of the catalyst concentrate obtained by filtering to the reaction kettle through the valve, sending the rest of the catalyst concentrate into a1 st washing kettle, and discharging the mixed clear liquid containing the epoxy chloropropane from a mixed clear liquid discharge port containing the epoxy chloropropane;
before the catalyst concentrate of the reaction kettle membrane filter is sent into the 1 st washing kettle, fresh solvent is firstly sent into the N th washing kettle from a fresh solvent feed port, and the catalyst concentrate is circulated to the 1 st washing kettle step by step;
the catalyst concentrate fed by the reaction kettle membrane filter and the circulating solvent clear liquid returned by the 2 nd washing kettle are mixed in the 1 st washing kettle, and then are fed into the 1 st washing kettle membrane filter for filtration and back flushing through a circulating pump, most of the catalyst concentrate obtained by filtration is returned to the 1 st washing kettle, the rest of the catalyst concentrate is fed into the 2 nd washing kettle, and the mixed clear liquid containing epoxy chloropropane is discharged from a mixed clear liquid discharge port containing epoxy chloropropane;
And so on;
The catalyst concentrate fed into the N-1-th washing kettle through the N-1-th washing kettle membrane filter is mixed with the fresh solvent fed from the fresh solvent feed inlet, and then fed into the N-th washing kettle membrane filter through a circulating pump for filtering and back flushing, the clear liquid of the circulating solvent obtained by filtering is returned to the N-1-th washing kettle, most of the catalyst concentrate is returned to the N-th washing kettle, and the rest of the catalyst concentrate is fed into a regeneration kettle;
And (3) after the catalyst concentrated solution fed in by the Nth set of washing kettle membrane filter is subjected to a regeneration reaction in the regeneration kettle, discharging the regenerated catalyst concentrated solution from a discharge port, and returning the regenerated catalyst concentrated solution to the reaction kettle through a regenerated catalyst concentrated solution feed port.
After a period of operation, a portion of the catalyst was discharged from the deactivated catalyst discharge port and a considerable amount of fresh catalyst was fed from the feed port of the reactor.
Preferably, the steam heating jackets are wrapped outside the reaction kettle and the regeneration kettle.
Preferably, stirring devices are arranged in the reaction kettle, the washing kettle and the regeneration kettle.
The technical scheme adopted by the invention for further solving the technical problems is as follows: the method for synthesizing epichlorohydrin and regenerating the catalyst on line comprises the following steps:
(1) Synthesis of epichlorohydrin: adding chloropropene, hydrogen peroxide, fresh solvent and catalyst into a reaction kettle for synthesis reaction, regulating the pH value of a reaction system with ammonia gas in the reaction process to be neutral to obtain a catalyst concentrate containing epichlorohydrin, sending the catalyst concentrate into a reaction kettle membrane filter for filtering and back flushing to obtain a mixed clear solution and a catalyst concentrate containing epichlorohydrin, returning most of the catalyst concentrate to the reaction kettle, and sending the rest of the catalyst concentrate into a1 st washing kettle;
(2) On-line cleaning of the catalyst:
Before the catalyst concentrate of the reaction kettle membrane filter is sent into the 1 st washing kettle, fresh solvent is firstly sent into the N-th washing kettle, and the catalyst concentrate is circulated to the 1 st washing kettle step by step;
Mixing the catalyst concentrate fed by the reaction kettle membrane filter with the circulating solvent clear liquid returned by the 2 nd washing kettle in the 1 st washing kettle, filtering and back flushing the mixture in the 1 st washing kettle membrane filter to obtain epoxy chloropropane mixed clear liquid and catalyst concentrate, returning most of the catalyst concentrate to the 1 st washing kettle, and feeding the rest of the catalyst concentrate into the 2 nd washing kettle;
And so on;
The catalyst concentrated solution sent into the N-1-th washing kettle by the N-1-th washing kettle membrane filter is mixed with fresh solvent, then sent into the N-th washing kettle membrane filter for filtering and back flushing to obtain circulating solvent clear solution and catalyst concentrated solution, the circulating solvent clear solution is returned to the N-1-th washing kettle, most of the catalyst concentrated solution is returned to the N-th washing kettle, and the rest of the catalyst concentrated solution is sent into the regeneration kettle;
(3) Regeneration of the catalyst: and (3) the catalyst concentrated solution fed in by the Nth set of washing kettle membrane filter is in a regeneration kettle, and after the regeneration reaction is carried out, the regenerated catalyst concentrated solution is returned to the reaction kettle.
Preferably, in the step (1), the molar ratio of the chloropropene to the hydrogen peroxide to the fresh solvent in the hydrogen peroxide is 0.9-6.0:1:3-4. The equation of the reaction of chloropropene and hydrogen peroxide is ：CH2ClCH=CH2 + H2O2→CH2ClCH-CH2(O) + H2O + Q., and the mass fraction of hydrogen peroxide used in the method is 27-50%. If the amount of chloropropene is too low, the conversion rate of chloropropene is low, and if the amount of chloropropene is too high, the circulation amount of chloropropene is large, and the energy consumption is high. If the dosage of the fresh solvent is too low, the oil-water compatibility is poor, the activity and the selectivity of the catalyst are affected, and if the dosage of the fresh solvent is too high, the solvent circulation amount is large, and the energy consumption is high. The process of the invention allows the feed equivalent to be adjusted according to the plant capacity at the indicated ratio.
Preferably, in the step (1), the mass concentration of the catalyst in the mixed system is 3-10%. If the concentration of the catalyst is too high, the load of the membrane filter is increased, the flux of the membrane filter is low, and if the concentration of the catalyst is too low, the activity and selectivity of the catalyst are low.
Preferably, in the step (1), the fresh solvent is one or more of methanol, ethanol, acetone or acetonitrile.
Preferably, in the step (1), the catalyst is titanium silicalite.
Preferably, the average particle diameter of the titanium silicalite molecular sieve is 0.1-0.3 μm.
Preferably, in the step (1), the temperature of the synthesis reaction is 40-120 ℃, the pressure is 0.2-0.8 MPa, and the time is 0.5-6.0 h.
Preferably, in the step (1), the neutral means that the pH value is 6-7.
Preferably, in the step (1), the volume ratio of the catalyst concentrate returned to the reaction kettle to the catalyst concentrate fed into the 1st set of washing kettle is 90-99:1-10. If a large amount of high-activity catalyst enters the reactor, the energy consumption is high, and if the proportion of the catalyst entering the reactor is small, the regenerated catalyst amount is small, and the activity and the selectivity of the catalyst in the reactor are low.
Preferably, in step (2), the fresh solvent is used in an amount corresponding to 0.5 to 3.0 times (more preferably 0.6 to 2.0 times) the volume of the catalyst concentrate intended to be fed to the 1 st pot set. If the amount of fresh solvent used for circulation is too small, the replacement of impurities such as epichlorohydrin in the catalyst is not clean, the regeneration effect is poor, and if the amount of clear solvent to be circulated is too large, the solvent circulation amount is large, and the energy consumption is high.
Preferably, in the step (2), the volume ratio of the catalyst concentrate returned to the 1 st washing kettle to the catalyst concentrate fed to the 2 nd washing kettle is 99.0-99.9:0.1-1.0. If the amount of the regenerated catalyst fed into the 2 nd washing kettle is large, the energy consumption is high, if the amount of the regenerated catalyst fed into the 2 nd washing kettle is small, the amount of the regenerated catalyst is small, the catalyst activity and the selectivity of the reaction kettle are low, and the production balance cannot be maintained.
Preferably, in the step (2), the volume ratio of the catalyst concentrate returned to the Nth washing kettle to the catalyst concentrate fed to the regeneration kettle is 99.0-99.9:0.1-1.0. If the amount of the catalyst concentrate fed into the regeneration kettle is too large, the energy consumption is high, and if the amount of the catalyst concentrate fed into the regeneration kettle is too small, the amount of the regenerated catalyst cannot be ensured, so that the activity and the selectivity of the catalyst of the reaction kettle are affected.
Preferably, in the steps (1) and (2), the transmembrane pressure difference of the filtration is less than or equal to 200kPa (more preferably 50-150 kPa), and the filtration is carried out until the concentration of the catalyst is concentrated to 3-5 times the mass concentration of the catalyst in the mixed system. If the filtration pressure difference is too high, the filter cake is thick and the flux is low.
Preferably, in the steps (1) and (2), the backflushing pressure difference of the backflushing is less than or equal to 500kPa. If the backflushing pressure difference is too high, the strength and the service life of the membrane tube can be influenced, and meanwhile, the energy consumption is high.
Preferably, in the step (3), the temperature of the regeneration reaction is 120-280 ℃, the pressure is 2-7 MPa, and the time is 20-100 h. The regeneration principle of the method is that the high-temperature solvent is soaked into the catalyst, so that impurities in the catalyst are dissolved out. If the temperature or pressure of the regeneration reaction is too low, the dissolution of impurities is incomplete, and if the temperature or pressure of the regeneration reaction is too high, the energy consumption is high.
Preferably, in the step (3), after the start-up, when one of the conversion rate or the selectivity of chloropropene or hydrogen peroxide is less than or equal to 95 percent (more preferably 90 to 95 percent), discharging a part of the catalyst returned to the reaction kettle by the regeneration kettle, and supplementing the fresh catalyst in the step (1).
Preferably, the catalyst is discharged in an amount corresponding to 2 to 8% (more preferably 4 to 6%) of the mass of the catalyst added in step (1).
Preferably, the additional fresh catalyst corresponds to 1 to 2 times the mass of the discharged catalyst.
According to the invention, the conversion rate and the selectivity data (namely the activity and the selectivity data of the catalyst) of chloropropene and hydrogen peroxide in the reaction kettle are obtained by carrying out timing sampling detection on the mixed clear liquid containing epichlorohydrin in the starting process.
The beneficial effects of the invention are as follows:
(1) The device has simple structure, the catalyst can be regenerated on line, the service life of the catalyst is long, the cost is low, and the device is suitable for industrial production;
(2) The method has the following advantages:
1) The conversion rate of chloropropene is more than or equal to 99.5%, the selectivity is more than or equal to 94.5%, the conversion rate of hydrogen peroxide is more than or equal to 99.5%, and the selectivity is more than or equal to 95.0%; after three months of continuous production without stopping, the conversion rate of chloropropene is more than or equal to 90.0 percent, the selectivity is more than or equal to 93.0 percent, the conversion rate of hydrogen peroxide is more than or equal to 99.5 percent, and the selectivity is more than or equal to 94.0 percent; after the operation, when one of the conversion rate or the selectivity of the chloropropene or the hydrogen peroxide is less than or equal to 95%, discharging a part of deactivated catalyst, supplementing a corresponding fresh catalyst, and after three months of operation, ensuring that the conversion rate of the chloropropene is more than or equal to 99.5%, the selectivity is more than or equal to 94.0%, the conversion rate of the hydrogen peroxide is more than or equal to 99.5%, and the selectivity is more than or equal to 95.0%, wherein the catalyst is basically stable at the activity and selectivity level of the fresh catalyst;
2) The service life of the catalyst is long, the activity and the selectivity of the catalyst can still reach more than 90% of that of a fresh catalyst after the catalyst is washed and regenerated on line, and the use cost is low;
3) The reaction condition is mild;
4) The wastewater discharge amount is less, about 3-4% of the chlorohydrin method, the COD of the wastewater is low (less than 800 ppm), the wastewater meets the national direct discharge index, lime is not used in wastewater treatment, and the production of calcium chloride solid which is difficult to treat is avoided, so that the wastewater treatment method is environment-friendly.
Drawings
FIG. 1 is a schematic diagram of an apparatus for synthesizing epichlorohydrin and regenerating a catalyst on line according to examples 1 to 3 of the invention.
Detailed Description
The invention is further described below with reference to examples and figures.
The mass fraction of the hydrogen peroxide used in the embodiment of the invention is 27.5% or 50%; the titanium-silicon molecular sieve used in the embodiment of the invention is of the model TS-1, and is purchased from Nanjing Xianfeng nano material technology Co., ltd, and the average grain diameter is 0.2 mu m; the materials or chemicals used in the examples of the present invention, unless otherwise specified, were obtained by conventional commercial means.
According to the embodiment of the invention, the conversion rate and the selectivity data (namely the activity and the selectivity data of the catalyst) of chloropropene and hydrogen peroxide in the reaction kettle are obtained by carrying out timing sampling detection on the mixed clear liquid containing epichlorohydrin in the driving process.
Device examples 1 to 3 for the Synthesis of epichlorohydrin and on-line regeneration of the catalyst
As shown in fig. 1, the device comprises a reaction kettle 1, a 1# washing kettle 2, a 2# washing kettle 3 and a regeneration kettle 4;
The upper part of the reaction kettle 1 is provided with a feed inlet 1-1, the lower part is provided with a discharge outlet 1-2, the discharge outlet 1-2 is connected with a valve 1-4-1 through a circulating pump 1-3, the valve 1-4-1 is respectively connected with a cooler 1-5 and a reaction kettle membrane filter 1-6, the cooler 1-5 is connected with the feed inlet 1-1 of the reaction kettle 1, the catalyst concentrate discharge outlet 1-6-1 of the reaction kettle membrane filter 1-6 is respectively connected with the feed inlet 1-1 of the reaction kettle 1 and a catalyst concentrate feed inlet 2-1 arranged at the upper part of a No. 1 washing kettle 2 through a valve 1-4-2, and the clear liquid side of the reaction kettle membrane filter 1-6 is provided with a mixed clear liquid discharge outlet 1-6-2 and a backflushing liquid feed inlet 1-6-3 containing epoxy chloropropane;
The lower part of the No. 1 kettle 2 is provided with a discharge port 2-2, the discharge port 2-2 is connected with a No. 1 kettle-washing membrane filter 2-4 through a circulating pump 2-3, a catalyst concentrate discharge port 2-4-1 of the No. 1 kettle-washing membrane filter 2-4 is respectively connected with a catalyst concentrate circulating feed port 2-5 arranged at the upper part of the No. 1 kettle-washing 2 and a catalyst concentrate feed port 3-6 arranged at the upper part of the No. 2 kettle-washing 3, and a mixed clear liquid discharge port 2-4-2 containing epichlorohydrin and a back flushing liquid feed port 2-4-3 are arranged at the clear liquid side of the No. 1 kettle-washing membrane filter 2-4;
The upper part of the 2# kettle 3 is provided with a fresh solvent feed inlet 3-1, the lower part of the 2# kettle 3 is provided with a discharge outlet 3-2, the discharge outlet 3-2 is connected with a 2# kettle-washing membrane filter 3-4 through a circulating pump 3-3, the catalyst concentrate discharge outlet 3-4-1 of the 2# kettle-washing membrane filter 3-4 is respectively connected with a catalyst concentrate circulating feed inlet 3-5 arranged at the upper part of the 2# kettle-washing 3 and a catalyst concentrate feed inlet 4-1 arranged at the upper part of the regeneration kettle 4, the circulating solvent clear liquid discharge outlet 3-4-2 arranged on the 2# kettle-washing membrane filter 3-4 is connected with a circulating solvent clear liquid feed inlet 2-6 arranged at the upper part of the 1# kettle-2, and the clear liquid side of the 2# kettle-washing membrane filter 3-4 is provided with a backflushing liquid feed inlet 3-4-3;
The discharge port 4-2 at the lower part of the regeneration kettle 4 is connected with the regenerated catalyst concentrated solution feed port 1-7 at the upper part of the reaction kettle 1; an inactive catalyst discharging outlet 4-3 is arranged on a pipeline between the regeneration kettle 4 and the reaction kettle 1;
the outsides of the reaction kettle 1 and the regeneration kettle 4 are respectively wrapped with steam heating jackets 1-8 and 4-4; stirring devices 1-9, 2-7, 3-7 and 4-5 are respectively arranged in the reaction kettle 1, the 1# kettle 2, the 2# kettle 3 and the regeneration kettle 4.
The technical process of the device of the invention is as follows: adding chloropropene, hydrogen peroxide, fresh solvent and catalyst into a reaction kettle 1 from a feed port 1-1, regulating the pH value of a reaction system by using ammonia gas, and carrying out a synthetic reaction, wherein part of reaction materials enter a cooler 1-5 from a discharge port 1-2 through a circulating pump 1-3 and a valve 1-4-1 for cooling and then return to the feed port 1-1 in the reaction process; after the reaction is stable, sending the catalyst concentrate containing the epoxy chloropropane into a reaction kettle membrane filter 1-6 through a valve 1-4-1, filtering and back flushing, returning most of the catalyst concentrate obtained by filtering to the reaction kettle 1 through a valve 1-4-2, sending the rest of the catalyst concentrate into a 1# washing kettle 2, and discharging the mixed clear liquid containing the epoxy chloropropane from a mixed clear liquid discharge port 1-6-2 containing the epoxy chloropropane;
Before the catalyst concentrate of the reaction kettle membrane filter 1-6 is sent into the No.1 kettle 2, fresh solvent is sent into the No. 2 kettle 3 from the fresh solvent feed port 3-1, and the catalyst concentrate circulates to the No.1 kettle 2;
The catalyst concentrated solution fed by the reaction kettle membrane filter 1-6 is mixed with the circulating solvent clear solution returned by the 2# kettle washing 3, and then fed into the 1# kettle washing membrane filter 2-4 through the circulating pump 2-3 for filtering and back flushing, most of the catalyst concentrated solution obtained by filtering is returned to the 1# kettle washing 2, the rest of the catalyst concentrated solution is fed into the 2# kettle washing 3, and the mixed clear solution containing epichlorohydrin is discharged from the mixed clear solution discharge port 2-4-2 containing epichlorohydrin;
And so on;
The catalyst concentrate fed into the 2# reactor 3 from the 1# reactor membrane filter 2-4 is mixed with fresh solvent fed from a fresh solvent feed port 3-1, and then fed into the 2# reactor membrane filter 3-4 through a circulating pump 3-3 for filtering and back flushing, the clear liquid of the circulating solvent obtained by filtering is returned to the 1# reactor 2, most of the catalyst concentrate is returned to the 2# reactor 3, and the rest of the catalyst concentrate is fed into a regeneration kettle 4;
The catalyst concentrate fed by the 2# reactor washing membrane filter 3-4 is discharged from the discharge port 4-2 after undergoing a regeneration reaction in the regeneration reactor 4, and is returned to the reaction reactor 1 through the regenerated catalyst concentrate feed port 1-7.
After a period of operation, a portion of the catalyst is discharged from the deactivated catalyst discharge port 4-3 and a considerable amount of fresh catalyst is fed from the feed port 1-1 of the reaction vessel 1.
Method for Synthesis of epichlorohydrin and on-line regeneration of catalyst example 1
(1) Synthesis of epichlorohydrin: the preparation method comprises the steps of adding chloropropene, hydrogen peroxide, methanol and titanium silicalite molecular sieves into a reaction kettle 1 respectively at 7.27t/h (95 kmol/h), 12.37t/h (27.5 wt%,100 kmol/h), 9.61t/h (300 kmol/h) and 3% of mass concentration (the total mass of the catalyst is 2.1 t) in a mixed system, carrying out synthesis reaction for 0.5h at 120 ℃ and 0.4MPa, regulating the pH value of the reaction system to be 7 by using ammonia gas in the reaction process, obtaining a catalyst concentrate containing epichlorohydrin, sending the catalyst concentrate into a reaction kettle membrane filter 1-6, filtering to the concentration of the catalyst to 15% under the transmembrane pressure difference of 50-150 kPa, carrying out back flushing under the back flushing pressure of less than or equal to 500kPa, obtaining mixed clear liquid and catalyst concentrate containing epichlorohydrin, and sending the catalyst concentrate with 99% of volume percent into a 1# washing kettle 2;
(2) On-line cleaning of the catalyst:
before the catalyst concentrate of the reaction kettle membrane filter 1-6 is sent into the No. 1 kettle 2, fresh solvent methanol which is 1.0 times of the volume of the catalyst concentrate planned to be sent into the No. 1 kettle 2 is sent into the No. 2 kettle 3, and the catalyst concentrate is circulated to the No. 1 kettle 2;
mixing the catalyst concentrated solution sent by the reaction kettle membrane filter 1-6 with the circulating solvent clear solution returned by the No.2 kettle 2, sending the mixture into the No.1 kettle 2-4 kettle membrane filter, filtering until the concentration of the catalyst is concentrated to 15% under the transmembrane pressure difference of 50-150 kPa, back flushing the mixture under the back flushing pressure of less than or equal to 500kPa to obtain epoxy chloropropane mixed clear solution and catalyst concentrated solution, returning the catalyst concentrated solution with the volume percentage of 99.9% to the No.1 kettle 2, and sending the catalyst concentrated solution with the volume percentage of 0.1% into the No.2 kettle 3;
And so on;
The catalyst concentrate sent into a 2# reactor 3 from a 1# reactor membrane filter 2-4 is mixed with fresh solvent methanol, then sent into the 2# reactor membrane filter 3-4, filtered until the concentration of the catalyst is concentrated to 15% under the transmembrane pressure difference of 50-150 kPa, back-washed under the back-flushing pressure of less than or equal to 500kPa to obtain circulating solvent clear liquid and catalyst concentrate, the circulating solvent clear liquid is returned to the 1# reactor 2, the catalyst concentrate with the volume percentage of 99.8% is returned to the 2# reactor, and the catalyst concentrate with the volume percentage of 0.2% is sent into a regeneration reactor 4;
(3) Regeneration of the catalyst: the catalyst concentrate fed in from the 2# reactor membrane filter 3-4 is subjected to a regeneration reaction for 20 hours at 120 ℃ and 2.0MPa in the regeneration reactor 4, and then the regenerated catalyst concentrate is returned to the reaction reactor 1.
Through detection, the conversion rate of chloropropene in the mixed clear liquid containing epichlorohydrin is 99.5%, and the selectivity is 96.5%; the conversion rate of hydrogen peroxide is 99.5% and the selectivity is 95.0%.
After continuous production for three months without stopping, the detection shows that the conversion rate of chloropropene in the mixed clear liquid containing epichlorohydrin is 97.0%, the selectivity is 93.0%, the conversion rate of hydrogen peroxide is 99.5%, and the selectivity is 94.0%.
After one month and two half months of driving (the selectivity of chloropropene is 94.5 percent and 95.0 percent respectively), 100kg of deactivated catalyst is discharged respectively, 150kg of fresh catalyst is supplemented, and after three months of operation, the conversion rate of chloropropene in the mixed clear liquid containing epoxy chloropropane is 99.5 percent, the selectivity is 96.5 percent, the conversion rate of hydrogen peroxide is 99.5 percent and the selectivity is 95.0 percent.
Method for Synthesis of epichlorohydrin and on-line regeneration of catalyst example 2
(1) Synthesis of epichlorohydrin: the preparation method comprises the steps of adding chloropropene, hydrogen peroxide, ethanol and titanium silicalite molecular sieves into a reaction kettle 1 at 40 ℃ and 0.2MPa respectively according to the mass concentration of 10% in a mixed system (the total mass of the catalyst is 7 t) in 22.96t/h (300 kmol/h), 10.20t/h (50 wt%,150 kmol/h) and 27.64t/h (600 kmol/h), carrying out synthesis reaction for 6.0h, regulating the pH value of the reaction system to 7 by using ammonia gas in the reaction process, obtaining a catalyst concentrate containing epichlorohydrin, sending the catalyst concentrate into a reaction kettle membrane filter 1-6, filtering until the concentration of the catalyst is concentrated to 30% under the transmembrane pressure of 50-150 kPa, carrying out back flushing under the back flushing pressure of less than or equal to 500kPa, obtaining a mixed clear liquid containing epichlorohydrin and a catalyst concentrate, and sending the catalyst concentrate with the volume percentage of 90% into a 1# washing kettle 2;
(2) On-line cleaning of the catalyst:
before the catalyst concentrate of the reaction kettle membrane filter 1-6 is sent into the No. 1 kettle 2, fresh solvent ethanol which is 1.5 times of the volume of the catalyst concentrate planned to be sent into the No. 1 kettle 2 is sent into the No. 2 kettle 3, and the catalyst concentrate is circulated to the No. 1 kettle 2;
mixing the catalyst concentrated solution sent by the reaction kettle membrane filter 1-6 with the circulating solvent clear solution returned by the No.2 kettle 2, sending the mixture into the No.1 kettle 2-4 kettle membrane filter, filtering until the concentration of the catalyst is concentrated to 30% under the transmembrane pressure difference of 50-150 kPa, back flushing the mixture under the back flushing pressure of less than or equal to 500kPa to obtain epoxy chloropropane mixed clear solution and catalyst concentrated solution, returning the catalyst concentrated solution with the volume percentage of 99.0% to the No.1 kettle 2, and sending the catalyst concentrated solution with the volume percentage of 1.0% into the No.2 kettle 3;
And so on;
The catalyst concentrate sent into a 2# reactor 3 from a 1# reactor membrane filter 2-4 is mixed with fresh solvent ethanol, then sent into the 2# reactor membrane filter 3-4, filtered until the concentration of the catalyst is concentrated to 30% under the transmembrane pressure difference of 50-150 kPa, back-washed under the back-flushing pressure of less than or equal to 500kPa to obtain circulating solvent clear liquid and catalyst concentrate, the circulating solvent clear liquid is returned to the 1# reactor 2, the catalyst concentrate with the volume percentage of 99.7% is returned to the 2# reactor, and the catalyst concentrate with the volume percentage of 0.3% is sent into a regeneration reactor 4;
(3) Regeneration of the catalyst: the catalyst concentrate fed in from the 2# reactor membrane filter 3-4 is subjected to a regeneration reaction for 100 hours at 280 ℃ and 7.0MPa in the regeneration reactor 4, and then the regenerated catalyst concentrate is returned to the reaction reactor 1.
Through detection, the conversion rate of chloropropene in the mixed clear liquid containing epichlorohydrin is 99.5%, and the selectivity is 95.5%; the conversion rate of hydrogen peroxide is 99.5% and the selectivity is 97.0%.
After continuous production for three months without stopping, the detection shows that the conversion rate of chloropropene in the mixed clear liquid containing epichlorohydrin is 91.0%, the selectivity is 93.0%, the conversion rate of hydrogen peroxide is 99.5%, and the selectivity is 94.0%.
After two months of operation (the conversion rate of chloropropene is 93.0 percent, the 300kg of deactivated catalyst is discharged, and 300kg of fresh catalyst is supplemented, and after three months of operation, the conversion rate of chloropropene in the mixed clear liquid containing epoxy chloropropane is 99.5 percent, the selectivity is 95.0 percent, the conversion rate of hydrogen peroxide is 99.5 percent, and the selectivity is 95.0 percent.
Method for Synthesis of epichlorohydrin and on-line regeneration of catalyst example 3
(1) Synthesis of epichlorohydrin: adding a mixture of chloropropene, hydrogen peroxide, acetonitrile and methanol in a mass ratio of 1:1 and a titanium silicalite molecular sieve into a reaction kettle 1 respectively at 36.73t/h (480 kmol/h), 9.90t/h (27.5 wt%,80 kmol/h) and 11.52t/h (320 kmol/h) which are equivalent to 5% of the mass concentration in the mixed system (the total mass of the catalyst is 3.5 t), carrying out a synthetic reaction for 3.0h at 60 ℃ and 0.8MPa, regulating the pH value of the reaction system to 7 by using gas ammonia in the reaction process to obtain a catalyst concentrate containing epichlorohydrin, sending the catalyst concentrate into a reaction kettle membrane filter 1-6, concentrating the catalyst concentrate to 25% under a transmembrane pressure difference of 50-150 kPa, carrying out back flushing under a back flushing pressure of less than or equal to 500kPa to obtain a mixed clear liquid containing epichlorohydrin and a catalyst concentrate, and sending the catalyst concentrate with 95% of which is subjected to volume percent into a 1# kettle 2;
(2) On-line cleaning of the catalyst:
Before the catalyst concentrate of the reaction kettle membrane filter 1-6 is sent to the No. 1 kettle 2, fresh solvent (a mixture of acetonitrile and methanol in a mass ratio of 1:1) which is 0.6 times of the volume of the catalyst concentrate planned to be sent to the No. 1 kettle 2 is sent to the No.2 kettle 3, and the catalyst concentrate is circulated to the No. 1 kettle 2;
mixing the catalyst concentrated solution sent by the reaction kettle membrane filter 1-6 with the circulating solvent clear solution returned by the No.2 kettle 2, sending the mixture into the No.1 kettle 2-4 kettle membrane filter, filtering the mixture until the concentration of the catalyst is concentrated to 25% under the transmembrane pressure difference of 50-150 kPa, back flushing the mixture under the back flushing pressure of less than or equal to 500kPa to obtain epoxy chloropropane mixed clear solution and catalyst concentrated solution, returning the catalyst concentrated solution with the volume percentage of 99.5% to the No.1 kettle 2, and sending the catalyst concentrated solution with the volume percentage of 0.5% into the No.2 kettle 3;
And so on;
the catalyst concentrate sent into a 2# kettle 3 from a 1# kettle-washing membrane filter 2-4 is mixed with fresh solvent (the mixture of acetonitrile and methanol in a mass ratio of 1:1), then sent into the 2# kettle-washing membrane filter 3-4, filtered until the concentration of the catalyst is concentrated to 25% under the transmembrane pressure difference of 50-150 kPa, back-washed under the back-flushing pressure of less than or equal to 500kPa to obtain circulating solvent clear liquid and catalyst concentrate, the circulating solvent clear liquid is returned to the 1# kettle 2, the catalyst concentrate with the volume percentage of 99.9% is returned to the 2# kettle, and the catalyst concentrate with the volume percentage of 0.1% is sent into a regeneration kettle 4;
(3) Regeneration of the catalyst: the catalyst concentrate fed in from the 2# reactor membrane filter 3-4 is regenerated in a regeneration reactor 4 at 170 ℃ and 3.5MPa for 40 hours, and then the regenerated catalyst concentrate is returned to the reaction reactor 1.
Through detection, the conversion rate of chloropropene in the mixed clear liquid containing epichlorohydrin is 99.5%, and the selectivity is 94.5%; the conversion rate of hydrogen peroxide is 99.5% and the selectivity is 96.0%.
After continuous production for three months without stopping, the detection shows that the conversion rate of chloropropene in the mixed clear liquid containing epichlorohydrin is 90.0%, the selectivity is 94.0%, the conversion rate of hydrogen peroxide is 99.5%, and the selectivity is 94.0%.
After one half month of start-up (the conversion rate of chloropropene is the lowest and is 95.0%), 200kg of deactivated catalyst is discharged, 400kg of fresh catalyst is supplemented, and after three months of operation, the conversion rate of chloropropene in the mixed clear liquid containing epoxy chloropropane is 99.5%, the selectivity is 94.0%, the conversion rate of hydrogen peroxide is 99.5% and the selectivity is 95.0% through detection.
Claims (19)
1. The utility model provides a device of synthesis of epoxy chloropropane and online regeneration of catalyst which characterized in that: comprises a reaction kettle, an N-set washing kettle and a regeneration kettle, wherein N is more than or equal to 2;
the upper part of the reaction kettle is provided with a feed inlet, the lower part of the reaction kettle is provided with a discharge outlet, the discharge outlet is connected with a valve through a circulating pump, the valve is respectively connected with a cooler and a reaction kettle membrane filter, the cooler is connected with the feed inlet of the reaction kettle, a catalyst concentrate discharge outlet of the reaction kettle membrane filter is respectively connected with the feed inlet of the reaction kettle and a catalyst concentrate feed inlet arranged at the upper part of the first washing kettle through a valve, and the clear liquid side of the reaction kettle membrane filter is provided with a mixed clear liquid discharge outlet containing epichlorohydrin and a backflushing liquid feed inlet;
The lower part of the 1 st washing kettle is provided with a discharge hole, the discharge hole is connected with the 1 st washing kettle membrane filter through a circulating pump, the catalyst concentrate discharge hole of the 1 st washing kettle membrane filter is respectively connected with a catalyst concentrate circulating feed hole arranged at the upper part of the 1 st washing kettle and a catalyst concentrate feed hole arranged at the upper part of the 2 nd washing kettle, and the clear liquid side of the 1 st washing kettle membrane filter is provided with a mixed clear liquid discharge hole containing epichlorohydrin and a backflushing liquid feed hole;
And so on;
The upper part of the Nth set of washing kettle is provided with a fresh solvent feed inlet, the lower part of the Nth set of washing kettle is provided with a discharge port, the discharge port is connected with the Nth set of washing kettle membrane filter through a circulating pump, the catalyst concentrate discharge port of the Nth set of washing kettle membrane filter is respectively connected with a catalyst concentrate circulating feed inlet arranged at the upper part of the Nth set of washing kettle and a catalyst concentrate feed inlet arranged at the upper part of the regeneration kettle, the circulating solvent clear liquid discharge port arranged on the Nth set of washing kettle membrane filter is connected with a circulating solvent clear liquid feed inlet arranged at the upper part of the N-1 th set of washing kettle, and the clear liquid side of the Nth set of washing kettle membrane filter is provided with a recoil liquid feed inlet;
the discharge port at the lower part of the regeneration kettle is connected with the regenerated catalyst concentrated solution feed port at the upper part of the reaction kettle; and an inactive catalyst discharging outlet is arranged on a pipeline between the regeneration kettle and the reaction kettle.
2. The apparatus for synthesizing epichlorohydrin and regenerating catalyst on line according to claim 1, characterized in that: steam heating jackets are wrapped outside the reaction kettle and the regeneration kettle; stirring devices are arranged in the reaction kettle, the washing kettle and the regeneration kettle.
3. A method for synthesizing epichlorohydrin and regenerating a catalyst on line by using the device as claimed in claim 1 or 2, characterized by comprising the following steps:
(1) Synthesis of epichlorohydrin: adding chloropropene, hydrogen peroxide, fresh solvent and catalyst into a reaction kettle for synthesis reaction, regulating the pH value of a reaction system with ammonia gas in the reaction process to be neutral to obtain a catalyst concentrate containing epichlorohydrin, sending the catalyst concentrate into a reaction kettle membrane filter for filtering and back flushing to obtain a mixed clear solution and a catalyst concentrate containing epichlorohydrin, returning most of the catalyst concentrate to the reaction kettle, and sending the rest of the catalyst concentrate into a1 st washing kettle;
(2) On-line cleaning of the catalyst:
Before the catalyst concentrate of the reaction kettle membrane filter is sent into the 1 st washing kettle, fresh solvent is firstly sent into the N-th washing kettle, and the catalyst concentrate is circulated to the 1 st washing kettle step by step;
Mixing the catalyst concentrate fed by the reaction kettle membrane filter with the circulating solvent clear liquid returned by the 2 nd washing kettle in the 1 st washing kettle, filtering and back flushing the mixture in the 1 st washing kettle membrane filter to obtain epoxy chloropropane mixed clear liquid and catalyst concentrate, returning most of the catalyst concentrate to the 1 st washing kettle, and feeding the rest of the catalyst concentrate into the 2 nd washing kettle;
And so on;
The catalyst concentrated solution sent into the N-1-th washing kettle by the N-1-th washing kettle membrane filter is mixed with fresh solvent, then sent into the N-th washing kettle membrane filter for filtering and back flushing to obtain circulating solvent clear solution and catalyst concentrated solution, the circulating solvent clear solution is returned to the N-1-th washing kettle, most of the catalyst concentrated solution is returned to the N-th washing kettle, and the rest of the catalyst concentrated solution is sent into the regeneration kettle;
(3) Regeneration of the catalyst: and (3) the catalyst concentrated solution fed in by the Nth set of washing kettle membrane filter is in a regeneration kettle, and after the regeneration reaction is carried out, the regenerated catalyst concentrated solution is returned to the reaction kettle.
4. The method for synthesizing epichlorohydrin and regenerating catalyst on line according to claim 3, characterized in that: in the step (1), the mol ratio of the hydrogen peroxide in the chloropropene and the hydrogen peroxide to the fresh solvent is 0.9-6.0:1:3-4; the mass concentration of the catalyst in the mixed system is 3-10%; the fresh solvent is one or more of methanol, ethanol, acetone or acetonitrile; the catalyst is titanium silicalite molecular sieve; the average grain diameter of the titanium silicalite molecular sieve is 0.1-0.3 mu m.
5. The method for synthesizing epichlorohydrin and regenerating catalyst on line according to claim 3 or 4, characterized in that: in the step (1), the temperature of the synthesis reaction is 40-120 ℃, the pressure is 0.2-0.8 MPa, and the time is 0.5-6.0 h; the volume ratio of the catalyst concentrated solution returned to the reaction kettle to the catalyst concentrated solution fed into the 1 st washing kettle is 90-99:1-10.
6. The method for synthesizing epichlorohydrin and regenerating catalyst on line according to claim 3 or 4, characterized in that: in the step (2), the dosage of the fresh solvent is 0.5 to 3.0 times of the volume of the catalyst concentrated solution planned to be fed into the 1 st washing kettle; the volume ratio of the catalyst concentrated solution returned to the 1 st washing kettle to the catalyst concentrated solution fed to the 2 nd washing kettle is 99.0-99.9:0.1-1.0.
7. The method for synthesizing epichlorohydrin and regenerating catalyst on line according to claim 5, characterized in that: in the step (2), the dosage of the fresh solvent is 0.5 to 3.0 times of the volume of the catalyst concentrated solution planned to be fed into the 1 st washing kettle; the volume ratio of the catalyst concentrated solution returned to the 1 st washing kettle to the catalyst concentrated solution fed to the 2 nd washing kettle is 99.0-99.9:0.1-1.0.
8. The method for synthesizing epichlorohydrin and regenerating catalyst on line according to claim 3 or 4, characterized in that: in the step (2), the volume ratio of the catalyst concentrated solution returned to the Nth washing kettle and fed into the regeneration kettle is 99.0-99.9:0.1-1.0.
9. The method for synthesizing epichlorohydrin and regenerating catalyst on line according to claim 5, characterized in that: in the steps (1) and (2), the transmembrane pressure difference of the filtration is less than or equal to 200kPa, and the filtration is carried out until the concentration of the catalyst is concentrated to be 3 to 5 times of the mass concentration of the catalyst in the mixed system; the backflushing pressure difference of the backflushing is less than or equal to 500kPa.
10. The method for synthesizing epichlorohydrin and regenerating catalyst on line according to claim 6, characterized in that: in the steps (1) and (2), the transmembrane pressure difference of the filtration is less than or equal to 200kPa, and the filtration is carried out until the concentration of the catalyst is concentrated to be 3 to 5 times of the mass concentration of the catalyst in the mixed system; the backflushing pressure difference of the backflushing is less than or equal to 500kPa.
11. The method for synthesizing epichlorohydrin and regenerating catalyst on line according to claim 3 or 4, characterized in that: in the step (3), the temperature of the regeneration reaction is 120-280 ℃, the pressure is 2-7 MPa, and the time is 20-100 h.
12. The method for synthesizing epichlorohydrin and regenerating catalyst on line according to claim 5, characterized in that: in the steps (1) and (2), the transmembrane pressure difference of the filtration is less than or equal to 200kPa, and the filtration is carried out until the concentration of the catalyst is concentrated to be 3 to 5 times of the mass concentration of the catalyst in the mixed system; the backflushing pressure difference of the backflushing is less than or equal to 500kPa.
13. The method for synthesizing epichlorohydrin and regenerating catalyst on line according to claim 6, characterized in that: in the steps (1) and (2), the transmembrane pressure difference of the filtration is less than or equal to 200kPa, and the filtration is carried out until the concentration of the catalyst is concentrated to be 3 to 5 times of the mass concentration of the catalyst in the mixed system; the backflushing pressure difference of the backflushing is less than or equal to 500kPa.
14. The method for synthesizing epichlorohydrin and regenerating catalyst on line according to claim 8, characterized in that: in the steps (1) and (2), the transmembrane pressure difference of the filtration is less than or equal to 200kPa, and the filtration is carried out until the concentration of the catalyst is concentrated to be 3 to 5 times of the mass concentration of the catalyst in the mixed system; the backflushing pressure difference of the backflushing is less than or equal to 500kPa.
15. The method for synthesizing epichlorohydrin and regenerating catalyst on line according to claim 3 or 4, characterized in that: in the step (3), after starting, when one of the conversion rate or the selectivity of chloropropene or hydrogen peroxide is less than or equal to 95%, discharging part of the catalyst returned to the reaction kettle by the regeneration kettle, and supplementing a fresh catalyst in the step (1); the discharge amount of the catalyst is 2-8% of the mass of the catalyst added in the step (1); the added fresh catalyst is equivalent to 1 to 2 times of the mass of the discharged catalyst.
16. The method for synthesizing epichlorohydrin and regenerating catalyst on line according to claim 5, characterized in that: in the step (3), after starting, when one of the conversion rate or the selectivity of chloropropene or hydrogen peroxide is less than or equal to 95%, discharging part of the catalyst returned to the reaction kettle by the regeneration kettle, and supplementing a fresh catalyst in the step (1); the discharge amount of the catalyst is 2-8% of the mass of the catalyst added in the step (1); the added fresh catalyst is equivalent to 1 to 2 times of the mass of the discharged catalyst.
17. The method for synthesizing epichlorohydrin and regenerating catalyst on line according to claim 6, characterized in that: in the step (3), after starting, when one of the conversion rate or the selectivity of chloropropene or hydrogen peroxide is less than or equal to 95%, discharging part of the catalyst returned to the reaction kettle by the regeneration kettle, and supplementing a fresh catalyst in the step (1); the discharge amount of the catalyst is 2-8% of the mass of the catalyst added in the step (1); the added fresh catalyst is equivalent to 1 to 2 times of the mass of the discharged catalyst.
18. The method for synthesizing epichlorohydrin and regenerating catalyst on line according to claim 8, characterized in that: in the step (3), after starting, when one of the conversion rate or the selectivity of chloropropene or hydrogen peroxide is less than or equal to 95%, discharging part of the catalyst returned to the reaction kettle by the regeneration kettle, and supplementing a fresh catalyst in the step (1); the discharge amount of the catalyst is 2-8% of the mass of the catalyst added in the step (1); the added fresh catalyst is equivalent to 1 to 2 times of the mass of the discharged catalyst.
19. The method for synthesizing epichlorohydrin and regenerating catalyst on line according to claim 11, characterized in that: in the step (3), after starting, when one of the conversion rate or the selectivity of chloropropene or hydrogen peroxide is less than or equal to 95%, discharging part of the catalyst returned to the reaction kettle by the regeneration kettle, and supplementing a fresh catalyst in the step (1); the discharge amount of the catalyst is 2-8% of the mass of the catalyst added in the step (1); the added fresh catalyst is equivalent to 1 to 2 times of the mass of the discharged catalyst.
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