CN108409690A - A kind of production technology of 1,2- epoxy butanes - Google Patents
A kind of production technology of 1,2- epoxy butanes Download PDFInfo
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- CN108409690A CN108409690A CN201810141433.7A CN201810141433A CN108409690A CN 108409690 A CN108409690 A CN 108409690A CN 201810141433 A CN201810141433 A CN 201810141433A CN 108409690 A CN108409690 A CN 108409690A
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- fixed bed
- logistics
- heat
- bed reactor
- calandria type
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- 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
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
-
- 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
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Abstract
The present invention provides a kind of production technology of 1,2 epoxy butane.The production technology of 1,2 epoxy butanes includes the following steps：Logistics 2 is divided into logistics 3 and logistics 4 after the supercharging of 2 feed pump of logistics, logistics 4 after preheating with after the logistics 1 after supercharged of 1 feed pump of logistics mixes enter calandria type fixed bed reactor, logistics 3 enters heat-insulating fixed bed reactors after the reaction product mixing as the cold shock logistics of adjustment heat-insulating fixed bed reactors inlet temperature and after calandria type fixed bed reactor reacts, logistics after the reaction of heat-insulating fixed bed reactors, as contain the reaction product of 1,2 epoxy butanes.The present invention passes through calandria type fixed bed reactor (level-one) and heat-insulating fixed bed reactors (two level) cascaded structure, it controls calandria type fixed bed reactor and heat-insulating fixed bed reactors Wen Sheng and waits measures in reasonable range, reduce energy consumption, improve equipment safety, safety and environmental protection.
Description
Technical field：
The invention belongs to technical field of polymer materials, and in particular to the production technology of one kind 1,2- epoxy butanes.
Background technology：
Propylene oxide is important one of basic chemical industry logistics, mainly for the production of polyester, propylene glycol and all kinds of nonionics
Surfactant etc. is widely applied to the industries such as chemical industry, building, light industry, food and medicine, traditional production of propylene oxide work
Skill is chlorohydrination.
1,2-1,2- epoxy butane are similar to propylene oxide structure, all have oxygen-containing three-membered ring structures, and chemical property is active,
May be used as polyether polyols alcohol monomer, organic synthesis logistics and other synthetic materials intermediate.It, which can be also used for making, contains
Antioxidant, corrosion inhibitor and nonionic surface active agent of chloride etc. have wide in fine chemistry industry and petrochemical industry
General purposes.
As olefin epoxide, compared with ethylene oxide and propylene oxide, on molecular structure, 1,2- epoxy butane is gathered around
There is greater number of-CH2Functional group, when as monomer synthesizing polyether glycol, product has excellent hydrophobic performance,
Particularly suitable for certain outer surface waterproof coatings for requiring stringent building and equipment.Meanwhile with 1,2- epoxy butanes for singly
The synthesized polyurethane material of body copolymerization possesses excellent cold tolerance, especially suitable for weather severe cold area.
The industrial production of 1,2- epoxy butane be mainly derived from propylene oxide byproduct recycling, with cracking tail gas through chlorine
During alcoholization and saponification production propylene oxide, 1,2- epoxy butane bottom products are obtained, by rectifying tower reactor raffinate, from tower
50 DEG C~70 DEG C of fraction is collected in portion, and moisture is removed after condensation, obtains 1, the 2- epoxy butane finished products of content about 87%, if you need to
Higher purity is wanted, then needs to carry out the separation processes such as further rectifying.Currently, the domestic factory for producing 1,2- epoxy butanes not yet
Family, 1,2- epoxy butanes are essentially from two company of DOW Chemical and BASF in the market.
The problems such as being difficult to handle there are seriously polluted, salt due to chlorohydrination, as green, health develop into modernization
The important idea of work, developing a kind of 1, the 2- epoxy butanes production technology of green economy just becomes reasonably necessary.Currently, foreign countries one
In the epoxidation reaction of olefines technical process of a little company's exploitations, the epoxidation catalyst service life is 30~60 days, is needed to frequently replace
Catalyst unloads agent, and dress agent is costly, therefore most of techniques are connected using multistage (>=5) heat-insulating fixed bed reactors, are passed through
Control reactor inlet temperature and each reactor temperature liter realize the control to reaction, wherein between reactor region using air-cooled or
Water cooling withdraws reaction heat, and reaction heat does not efficiently use, and consumes a large amount of recirculated cooling water or electric energy, and control is complicated, and replacement is urged
Agent security risk is high.The technical problems such as that there are reactor quantity is more for technical process, control complexity, equipment investment height, high energy consumption.
Invention content：
The present invention provide one kind 1,2- epoxy butanes production technology, the present invention for reactor of the existing technology with
The problems such as control instrument quantity is more, and control is complicated, and reaction heat cannot utilize, high energy consumption, pass through calandria type fixed bed reactor (one
Grade) and heat-insulating fixed bed reactors (two level) cascaded structure, circulating hot water continuously withdraws reaction heat, controls shell and tube and fix
Bed reactor Wen Sheng waits measures in reasonable range, can reduce reactor quantity, and control is simple, reduces energy consumption, improves device
Safety, safety and environmental protection.
The object of the present invention is to provide the production technologies of one kind 1,2- epoxy butanes, include the following steps：Logistics 2 is passed through
Be divided into logistics 3 and logistics 4 after the supercharging of 2 feed pump of logistics, logistics 4 after preheating with pass through 1 feed pump of logistics object after supercharged
Enter calandria type fixed bed reactor after 1 mixing of stream, logistics 3, which is used as, to be used for adjusting heat-insulating fixed bed reactors inlet temperature
Cold shock logistics and after calandria type fixed bed reactor reacts reaction product mixing after enter heat-insulating fixed bed reaction
Device, the logistics after the reaction of heat-insulating fixed bed reactors, as contains the reaction product of 1,2- epoxy butanes, the object
Stream 1 is cumyl hydroperoxide or hydrogen peroxide ethylbenzene, and logistics 2 is 1- butylene, and calandria type fixed bed reactor and heat-insulating are solid
Ti-SBA-15 catalyst is loaded in fixed bed reactor.
The present invention uses calandria type fixed bed reactor (level-one) and heat-insulating fixed bed reactors (two level) cascaded structure,
Ti-SBA-15 molecular sieve catalysts are loaded in calandria type fixed bed reactor and heat-insulating fixed bed reactors.Ti-SBA-15 points
The service life of sub- sieve catalyst improved to >=180 days, and or so half a year replaces a catalyst, made to use calandria type fixed bed reactor
It becomes a reality, a calandria type fixed bed reactor can be used in first-stage reactor, and stop more catalyst changeout；First-stage reactor also may be used
Using two calandria type fixed bed reactor handover operations, wherein a calandria type fixed bed reactor more catalyst changeout, switching
To an other calandria type fixed bed reactor, the reaction was continued.
The synthesis of Ti-SBA-15 molecular sieve catalysts, under strongly acidic conditions, PEG-PPG-PPE non-ionic surface actives
Agent is template, and esters of silicon acis is silicon source, and hydrothermal synthesis method prepares SBA-15 original powders, wherein the esters of silicon acis is selected from positive silicic acid tetramethyl
Ester, tetraethyl orthosilicate, positive silicic acid orthocarbonate, acid preferably molar concentration is 1.5~4mol/L.With molar ratio computing, silicon source：
PEG-PPG-PPE：HCl:H2O=1:(0.01~0.045):(5~15):(40~150).
SBA-15 original powders and binder are shaped to carrier；The dosage of original powder is 50~99%.With halogenated titanium or titanate esters
It for titanium source, uses organic solvent in the form of liquid phase grafted branches, the active titanium species with four-coordination is implanted to the carrier of gained
In skeleton, titaniferous porous silica Si catalyst is obtained.The wherein described titanium source is titanium chloride, acetic acid titanium, tetramethoxy titanate ester, metatitanic acid
It is one or more in tetra-ethyl ester, butyl titanate.The wherein described organic solvent be methanol, ethyl alcohol and isopropanol in one kind or
It is a variety of.
Since Ti-SBA-15 molecular sieve surfaces also have abundant silicone hydroxyl and titanium hydroxyl, there is centainly acid and higher
Hydrophily in the presence of an organic, further obtain catalyst to above-mentioned to improve epoxidised selectivity and yield
Silanization treatment is carried out, catalyst surface hydrophobicity is enhanced.Wherein, organic solvent be selected from carbon atom number be 6~20 aromatic hydrocarbon,
It is one or more in chain hydrocarbon；Organosilicon is selected from least one of halosilanes, silazane or silylamine.With height
The weight percentage of titanium is 0.1%~15% in the titaniferous porous silica Si catalyst of hydrophobic property.
It is preferred that the 1- butylene is 6 with the molar ratio of cumyl hydroperoxide or hydrogen peroxide ethylbenzene：1~10：1.
With CHP or EBHP epoxidation reaction occurs for 1- butylene, and reaction heat 210kJ/mol is strong exothermal reaction, is effective
Reaction heat is removed in time, and calandria type fixed bed reactor generates low-pressure steam using hot water and removes reaction heat, and low-pressure steam can be made
For reaction or the heat source of later separation unit, reaction heat can be made full use of.
It is preferred that ensure cumyl hydroperoxide or hydrogen peroxide conversion of ethylbenzene close to conversion completely, the tubulation
Ti-SBA-15 loaded catalyst mass ratioes are 1 in formula fixed bed reactors and heat-insulating fixed bed reactors：1~1：5.
It is preferred that the calandria type fixed bed reactor reaction pressure be 2.5~4.0MPaG, reaction temperature be 40 DEG C~
130℃；The heat-insulating fixed bed reactors reaction pressure is 2.5~4.0MPaG, and reaction temperature is 60 DEG C~130 DEG C.Into
One step is preferred, and the calandria type fixed bed reactor reaction pressure is 2.8~3.3MPaG, and reaction temperature is 60 DEG C~130
℃；The heat-insulating fixed bed reactors reaction pressure is 3.0~3.5MPaG, and reaction temperature is 60 DEG C~130 DEG C.Tubulation
The reaction mass in circulating hot water and tube side in formula fixed bed reactors in shell side flows in the opposite direction, continuously withdraws from reaction
Heat makes temperature≤130 DEG C of the reaction mass in tube side.To ensure CHP (EBHP) selectivity and conversion ratio, shell and tube reactor
CHP (EBHP) stream liquid mass space velocity is 0.2~0.8m3/ h, further preferred shell and tube reactor CHP (EBHP) logistics liquid
Weight air speed is 0.40~0.65m3/h。
It is preferred that the calandria type fixed bed reactor side is provided with gas-liquid mixture circulation duct, gas-liquid mixture
Circulation duct is connected to drum, and circulating hot water outlet is provided on drum, and circulating hot water outlet is connected to circulating hot water pipeline, follows
Ring hot water pipeline one end is connected to drum, and the other end is by being arranged the circulating hot water entrance in calandria type fixed bed reactor lower part
It is connected to calandria type fixed bed reactor.The stream of reaction mass in calandria type fixed bed reactor and heat-insulating fixed bed reactors
To for upper entering and lower leaving, wherein calandria type fixed bed reactor tube side walks reaction mass, and shell side walks circulating hot water, bottom in and top out, vapour
Packet is equivalent to gas-liquid separator, and circulating hot water continuously withdraws the reaction heat in calandria type fixed bed reactor, makes full use of reaction
Heat, the low-pressure steam being discharged from the steam (vapor) outlet on drum can be used as the heat source of reaction member or later separation unit in device.
The calandria type fixed bed reactor outlet streams, a part are recycled to calandria type fixed bed reactor entrance,
Another part enters heat-insulating fixed bed reactors and participates in reaction.
Unless otherwise indicated, nominal definition of the present invention has is generally understood identical contain with those skilled in the art
Justice.
Compared with prior art, the present invention has the following advantages：The present invention passes through calandria type fixed bed reactor (one
Grade) and heat-insulating fixed bed reactors (two level) cascaded structure, circulating hot water continuously withdraws reaction heat, controls calandria type fixed bed
Reactor Wen Sheng equal measures in reasonable range, can reduce reactor quantity, and control is simple, reduces energy consumption, improve device peace
Quan Xing, safety and environmental protection.
Description of the drawings：
Fig. 1 is a kind of process flow chart of the production technology of 1,2- epoxy butanes of the present invention；
Reference sign A, CHP/EBHP feed pump；B, 1- butene feeds pump；C, 1- butene feeds preheater；D, tubulation
Formula fixed bed reactors (first-stage reactor)；E, heat-insulating fixed bed reactors (second reactor)；F, circulating hot-water pump；G, vapour
Packet.
Specific implementation mode：
The following examples are further illustrations of the invention, rather than limiting the invention.In the present invention, tubulation
Formula fixed bed reactors are first-stage reactor, and heat-insulating fixed bed reactors are second reactor.Calandria type fixed bed reactor
Can be one or more calandria type fixed bed reactors to get up in parallel or series, heat-insulating fixed bed reactors can be one
It is solid just for a shell and tube in a or multiple heat-insulating fixed bed reactors to get up in parallel or series, embodiment and Fig. 1
The technological process that fixed bed reactor and a heat-insulating fixed bed reactors are used in series, the present invention are not limited in protecting Fig. 1
Shown in technological process.Arrow indicates logistics direction in Fig. 1.
Embodiment 1：
Technological process as shown in Figure 1, CHP logistics are pressurized to 2.8MPaG by CHP feed pumps A, and 1- butene streams pass through
1- butene feeds pump B is pressurized to 3.0MPaG, 1- butene streams after supercharged is divided into two strands, one 1- butene stream 4 passes through
It is calandria type fixed bed anti-with being mixed by CHP feed pumps A CHP logistics after supercharged after the C preheatings of 1- butene feed preheaters
Device D is answered, another strand of 1- butene stream is used for adjusting heat-insulating fixed bed reactors E inlet temperatures as cold shock logistics, and passes through
Enter heat-insulating fixed bed reactors E after reaction product mixing after calandria type fixed bed reactor D reactions, it is solid by heat-insulating
Logistics after the E reactions of fixed bed reactor, as contains the reaction product of 1,2- epoxy butanes.Circulating hot water passes through circulating hot-water pump
After F superchargings, from the lower parts first-stage reactor D shell side be divided to two strands it is symmetrical into first-stage reactor shell side, hot water after heating and gasifying,
Into drum G (interval is needed to supplement desalted water and oxygen scavenger and ten phosphate dihydrate sodium), drum G is equivalent to gas-liquid separator, low
Press steam from the steam (vapor) outlet discharge on drum G.
Calandria type fixed bed reactor D shell sides top is symmetrically arranged with gas-liquid mixture circulation duct, gas-liquid mixed logistics
It threads a pipe and is connected to drum G, circulating hot water outlet is provided on drum G, circulating hot water outlet is connected to circulating hot water pipeline, follows
Ring hot water pipeline one end is connected to drum G, and the other end is entered by the circulating hot water for being arranged in the lower parts calandria type fixed bed reactor D
Mouth is connected to calandria type fixed bed reactor D.Reactant in calandria type fixed bed reactor D and heat-insulating fixed bed reactors E
The flow direction of material is upper entering and lower leaving, and wherein calandria type fixed bed reactor D tube sides walk reaction mass, and shell side walks circulating hot water, under into
On go out, circulating hot water continuously withdraws the reaction heat in calandria type fixed bed reactor D, makes full use of reaction heat, from drum G
The low-pressure steam of steam (vapor) outlet discharge can be used as the heat source of reaction member or later separation unit in device.It is calandria type fixed bed anti-
Device D outlet streams, a part are answered to be recycled to calandria type fixed bed reactor D entrances, it is anti-that another part enters heat-insulating fixed bed
Device E is answered to participate in reaction.
The molar ratio of CHP is 6 in 1- butene streams and CHP logistics：1, wherein the mass concentration of CHP logistics be 30%~
60%, remaining ingredient is isopropylbenzene.Calandria type fixed bed reactor CHP stream liquid mass space velocities are 0.65m3/h.Shell and tube
Ti-SBA-15 loaded catalyst mass ratioes are 1 in fixed bed reactors and heat-insulating fixed bed reactors：2.
The Ti-SBA-15 molecular sieves of calandria type fixed bed reactor and the filling of heat-insulating fixed bed reactors in the present embodiment
Catalyst, specific synthesis step are as follows：
24g nonionic surfactants P123 is added in the aqueous hydrochloric acid solution of 600g 2mol/L, 1 is stirred at 35 DEG C
Hour, above-mentioned solution is added in 51.2g ethyl orthosilicates, is stirred 24 hours at 35 DEG C, said mixture is transferred to water heating kettle,
In 100 DEG C of hydrothermal crystallizings 24 hours.After hydro-thermal reaction, solid product is detached with mother liquor, is washed with deionized into
Property, obtain SBA-15 original powders within dry 3 hours at 110 DEG C.By the SBA-15 original powders of 20.0g and 200mL acidified methanols (methanol with it is dense
Hydrochloric acid volume ratio is 20:1) it mixes, in 80 DEG C of reflux extraction 10 hours, is then filtered, washed, the vacuum drying 3 at 120 DEG C
Hour obtains SBA-15 molecular sieves.
2.4g tetraisopropyl titanates are dissolved in 400g isopropanols, are mixed with the above-mentioned SBA-15 molecular sieves of 10.0g, in work(
It under the ultrasonic wave auxiliary that rate is 200W, is stirred to react 30 minutes, temperature is 30 DEG C.The solid production isolated is washed with isopropanol
Object, 5 hours dry at 90 DEG C, 350 DEG C roast 5 hours, obtain Ti-SBA-15 molecular sieves.
By above-mentioned technological process, calandria type fixed bed reactor reaction pressure is 2.8MPaG, and inlet temperature is 60 DEG C, is gone out
Mouth temperature is 130 DEG C.Heat-insulating fixed bed reactors reaction pressure is 3.0MPaG, and inlet temperature is 60 DEG C, calandria type fixed bed
Reactor catalyst initial stage, heat-insulating fixed bed reactors outlet temperature are 60 DEG C, latter stage, the outlet of heat-insulating fixed bed reactors
Temperature is 80 DEG C~100 DEG C.Setting cooler can be exported in calandria type fixed bed reactor, or thermal insulation is adjusted by cold 1- butylene
Formula fixed bed reactors inlet temperature.
The reaction mass in circulating hot water and tube side in calandria type fixed bed reactor in shell side flows in the opposite direction,
Continuous to withdraw from reaction heat, it is 130 DEG C that circulating hot water, which enters calandria type fixed bed reactor temperature, persistently generates 0.18MPaG low pressure
Steam, quantity of steam are 0.713 ton of steam/1 ton 1,2- epoxy butanes.The production technology of the 1,2- epoxy butanes of the present embodiment can be real
Existing calandria type fixed bed reactor and heat-insulating fixed bed reactors are normal, stablize, safety operation, while the conversion ratio of CHP >=
99.4%, 1,2- epoxy butane molar selectivity >=99.0%.
Embodiment 2：
It is same as Example 1, the difference is that：
Technological process as shown in Figure 1, EBHP logistics are pressurized to 3.0MPaG by EBHP feed pumps A, and 1- butene streams are logical
It crosses 1- butene feeds pump B and is pressurized to 3.2MPaG, 1- butene streams after supercharged are divided into two strands, one 1- butene stream passes through
It is calandria type fixed bed with being mixed by EBHP feed pumps A EBHP logistics after supercharged after the C preheatings of 1- butene feed preheaters
Reactor D, another strand of 1- butene stream is as cold shock logistics, for adjusting heat-insulating fixed bed reactors E inlet temperatures, and warp
Enter heat-insulating fixed bed reactors E after the reaction product mixing crossed after calandria type fixed bed reactor D reactions, by heat-insulating
Logistics after fixed bed reactors E reactions, as contains the reaction product of 1,2- epoxy butanes.
Circulating hot water is after circulating hot-water pump F superchargings, and from the lower parts first-stage reactor D, shell side is divided to two strands symmetrically to enter level-one
Reactor shell side, hot water (need interval to supplement desalted water and oxygen scavenger and 12 water phosphorus after heating and gasifying, into drum G
Sour sodium), drum G is equivalent to gas-liquid separator, and low-pressure steam is discharged from the steam (vapor) outlet on drum G.
Calandria type fixed bed reactor D shell sides top is symmetrically arranged with gas-liquid mixture circulation duct, gas-liquid mixed logistics
It threads a pipe and is connected to drum G, circulating hot water outlet is provided on drum G, circulating hot water outlet is connected to circulating hot water pipeline, follows
Ring hot water pipeline one end is connected to drum G, and the other end is entered by the circulating hot water for being arranged in the lower parts calandria type fixed bed reactor D
Mouth is connected to calandria type fixed bed reactor D.Reactant in calandria type fixed bed reactor D and heat-insulating fixed bed reactors E
The flow direction of material is upper entering and lower leaving, and wherein calandria type fixed bed reactor D tube sides walk reaction mass, and shell side walks circulating hot water, under into
On go out, circulating hot water continuously withdraws the reaction heat in calandria type fixed bed reactor D, makes full use of reaction heat, from drum G
The low-pressure steam of steam (vapor) outlet discharge can be used as the heat source of reaction member or later separation unit in device.
The molar ratio of EBHP is 6 in 1- butene streams and EBHP logistics：1, the wherein mass concentration of EBHP logistics is 30%
~60%, remaining ingredient is ethylbenzene, Ti-SBA-15 molecular sieves in calandria type fixed bed reactor and heat-insulating fixed bed reactors
Loaded catalyst mass ratio is 1：2.Calandria type fixed bed reactor EBHP stream liquid mass space velocities are 0.45m3/h。
Calandria type fixed bed reactor reaction pressure is 3.0MPaG, and inlet temperature is 70 DEG C, and outlet temperature is 130 DEG C.Absolutely
Hot type fixed bed reactors reaction pressure is 3.2MPaG, and inlet temperature is 60 DEG C, at the beginning of calandria type fixed bed reactor catalyst
Phase, heat-insulating fixed bed reactors outlet temperature be 60 DEG C, latter stage, heat-insulating fixed bed reactors outlet temperature be 80 DEG C~
100℃.Setting cooler can be exported in calandria type fixed bed reactor, or heat-insulating fixed bed reaction is adjusted by cold 1- butylene
Device inlet temperature.
The reaction mass in circulating hot water and tube side in calandria type fixed bed reactor in shell side flows in the opposite direction,
Continuous to withdraw from reaction heat, it is 130 DEG C that circulating hot water, which enters calandria type fixed bed reactor temperature, persistently generates 0.18MPaG low pressure
Steam, quantity of steam are 0.795 ton of steam/1 ton 1,2- epoxy butanes.
The production technology of the 1,2- epoxy butanes of the present embodiment can realize that calandria type fixed bed reactor and heat-insulating are fixed
Bed reactor is normal, stablizes, safety operation, while EBHP conversion ratios >=99.5%, 1, and 2- epoxy butanes molar selectivity >=
99.0%.
Embodiment 3：
It is same as Example 1, the difference is that：
Technological process as shown in Figure 1, CHP logistics are pressurized to 3.3MPaG by CHP feed pumps A, and 1- butene streams pass through
1- butene feeds pump B is pressurized to 3.5MPaG, 1- butene streams after supercharged is divided into two strands, one 1- butene stream 4 passes through
It is calandria type fixed bed anti-with being mixed by CHP feed pumps A CHP logistics after supercharged after the C preheatings of 1- butene feed preheaters
Device D, another strand of 1- butene stream is answered for adjusting heat-insulating fixed bed reactors E inlet temperatures, and to pass through as cold shock logistics
Enter heat-insulating fixed bed reactors E after reaction product mixing after calandria type fixed bed reactor D reactions, it is solid by heat-insulating
Logistics after the E reactions of fixed bed reactor, as contains the reaction product of 1,2- epoxy butanes.Circulating hot water passes through circulating hot-water pump
After F superchargings, from the lower parts first-stage reactor D shell side be divided to two strands it is symmetrical into first-stage reactor shell side, hot water after heating and gasifying,
Into drum G (interval is needed to supplement desalted water and oxygen scavenger and ten phosphate dihydrate sodium), drum G is equivalent to gas-liquid separator, low
Press steam from the steam (vapor) outlet discharge on drum G.
Calandria type fixed bed reactor D shell sides top is symmetrically arranged with gas-liquid mixture circulation duct, gas-liquid mixed logistics
It threads a pipe and is connected to drum G, circulating hot water outlet is provided on drum G, circulating hot water outlet is connected to circulating hot water pipeline, follows
Ring hot water pipeline one end is connected to drum G, and the other end is entered by the circulating hot water for being arranged in the lower parts calandria type fixed bed reactor D
Mouth is connected to calandria type fixed bed reactor D.Reactant in calandria type fixed bed reactor D and heat-insulating fixed bed reactors E
The flow direction of material is upper entering and lower leaving, and wherein calandria type fixed bed reactor D tube sides walk reaction mass, and shell side walks circulating hot water, under into
On go out, circulating hot water continuously withdraws the reaction heat in calandria type fixed bed reactor D, makes full use of reaction heat, from drum G
The low-pressure steam of steam (vapor) outlet discharge can be used as the heat source of reaction member or later separation unit in device.1- butene streams and
The molar ratio of CHP is 8 in CHP logistics：1, the wherein mass concentration of CHP logistics is 30%~60%, and remaining ingredient is isopropylbenzene.
Calandria type fixed bed reactor CHP stream liquid mass space velocities are 0.55m3/h.Calandria type fixed bed reactor and heat-insulating are solid
Fixed bed catalyst reactor loadings mass ratio is 1：1.5.
Calandria type fixed bed reactor reaction pressure is 3.3MPaG, and inlet temperature is 80 DEG C, and outlet temperature is 130 DEG C.Absolutely
Hot type fixed bed reactors reaction pressure is 3.5MPaG, and inlet temperature is 60 DEG C, at the beginning of calandria type fixed bed reactor catalyst
Phase, heat-insulating fixed bed reactors outlet temperature are 60 DEG C, and latter stage, heat-insulating fixed bed reactors outlet temperature is 80~100
℃.Setting cooler can be exported in calandria type fixed bed reactor, or heat-insulating fixed bed reactors are adjusted by cold 1- butylene
Inlet temperature.
The reaction mass in circulating hot water and tube side in calandria type fixed bed reactor in shell side flows in the opposite direction,
Continuous to withdraw from reaction heat, it is 130 DEG C that circulating hot water, which enters calandria type fixed bed reactor temperature, persistently generates 0.18MPaG low pressure
Steam, quantity of steam are 0.786 ton of steam/1 ton 1,2- epoxy butanes.
The production technology of the 1,2- epoxy butanes of the present embodiment can realize that calandria type fixed bed reactor and heat-insulating are fixed
Bed reactor is normal, stablizes, safety operation, while CHP conversion ratios >=99.6%, 1, and 2- epoxy butanes molar selectivity >=
99.0%.
Embodiment 4：
It is same as Example 1, the difference is that：
Technological process as shown in Figure 1,
CHP logistics is pressurized to 3.1MPaG by CHP feed pumps A, and 1- butene streams pump B by 1- butene feeds and are pressurized to
1- butene streams after supercharged are divided into two strands by 3.3MPaG, one 1- butene stream 4 is pre- by 1- butene feed preheaters C
After heat, calandria type fixed bed reactor D, another strand of 1- butylene are mixed by CHP feed pumps A CHP logistics after supercharged
Logistics for adjusting heat-insulating fixed bed reactors E inlet temperatures, and passes through calandria type fixed bed reactor as cold shock logistics
Enter heat-insulating fixed bed reactors E after reaction product mixing after D reactions, after the E reactions of heat-insulating fixed bed reactors
Logistics, as contain the reaction product of 1,2- epoxy butanes.Circulating hot water is anti-from level-one after circulating hot-water pump F superchargings
The lower parts device D shell side is answered to be divided to two strands symmetrically to enter first-stage reactor shell side, hot water (needs after heating and gasifying into drum G
Interval supplement desalted water and oxygen scavenger and ten phosphate dihydrate sodium), drum G is equivalent to gas-liquid separator, and low-pressure steam is from drum G
Steam (vapor) outlet discharge.
Calandria type fixed bed reactor D shell sides top is symmetrically arranged with gas-liquid mixture circulation duct, gas-liquid mixed logistics
It threads a pipe and is connected to drum G, circulating hot water outlet is provided on drum G, circulating hot water outlet is connected to circulating hot water pipeline, follows
Ring hot water pipeline one end is connected to drum G, and the other end is entered by the circulating hot water for being arranged in the lower parts calandria type fixed bed reactor D
Mouth is connected to calandria type fixed bed reactor D.Reactant in calandria type fixed bed reactor D and heat-insulating fixed bed reactors E
The flow direction of material is upper entering and lower leaving, and wherein calandria type fixed bed reactor D tube sides walk reaction mass, and shell side walks circulating hot water, under into
On go out, circulating hot water continuously withdraws the reaction heat in calandria type fixed bed reactor D, makes full use of reaction heat, from drum G
The low-pressure steam of steam (vapor) outlet discharge can be used as the heat source of reaction member or later separation unit in device.1- butene streams and
The molar ratio of CHP is 10 in CHP logistics：1, the wherein mass concentration of CHP logistics is 30%~60%, and remaining ingredient is isopropyl
Benzene.Calandria type fixed bed reactor CHP stream liquid mass space velocities are 0.40m3/h.Calandria type fixed bed reactor and heat-insulating
Loaded catalyst mass ratio is 1 in fixed bed reactors：1.
Calandria type fixed bed reactor reaction pressure is 3.1MPaG, and inlet temperature is 100 DEG C, and outlet temperature is 130 DEG C.
Heat-insulating fixed bed reactors reaction pressure is 3.3MPaG, and inlet temperature is 60 DEG C, at the beginning of calandria type fixed bed reactor catalyst
Phase, heat-insulating fixed bed reactors outlet temperature are 60 DEG C, and latter stage, heat-insulating fixed bed reactors outlet temperature is 80~100
℃.Setting cooler can be exported in calandria type fixed bed reactor, or heat-insulating fixed bed reactors are adjusted by cold 1- butylene
Inlet temperature.
The reaction mass in circulating hot water and tube side in calandria type fixed bed reactor in shell side flows in the opposite direction,
Continuous to withdraw from reaction heat, it is 130 DEG C that circulating hot water, which enters calandria type fixed bed reactor temperature, persistently generates 0.18MPaG low pressure
Steam, quantity of steam are 0.930 ton of steam/1 ton 1,2- epoxy butanes.
The production technology of the 1,2- epoxy butanes of the present embodiment can realize that calandria type fixed bed reactor and heat-insulating are fixed
Bed reactor is normal, stablizes, safety operation, while CHP conversion ratios >=99.62%, 1, and 2- epoxy butanes molar selectivity >=
99.0%.
Comparative example 1：
It is same as Example 4, the difference is that：
Calandria type fixed bed reactor D is changed to heat-insulating fixed bed reactors in technological process, is 2 heat-insulating fixed beds
Reactor E is connected in series with, and 1-1- butene streams after supercharged are divided into two strands, one 1- butene stream is pre- by 1- butene feeds
After hot device preheating, the first heat-insulating fixed bed reactors are mixed into CHP after supercharged, one 1- butylene cold shock is exhausted with first
Enter the second heat-insulating fixed bed reactors after the first order reaction product mixing of hot type fixed bed reactors, it is solid through the second heat-insulating
Second order reaction product after fixed bed reactor removes later separation unit, anti-after the reaction of the second heat-insulating fixed bed reactors
It is 1,2- epoxy butanes to answer product.First heat-insulating fixed bed reactors and the second heat-insulating fixed bed reactors model phase
Together, loading catalyst is identical in quality.
Temperature of the circulating hot water into and out of heat-insulating fixed bed reactors in the production technology of the 1,2- epoxy butanes of this comparative example
Difference is 8 DEG C, and it is 94 DEG C to enter heat-insulating fixed bed reactors hot water temperature, and it is 102 to go out heat-insulating fixed bed reactors hot water temperature
DEG C, pressure is 0.3MPaG (not generating low-pressure steam).CHP conversion ratios >=98.02%, 1,2- epoxy butanes molar selectivity >=
97.0%.
Comparative example 1 and the result of embodiment 4 compare, and two heat-insulating fixed bed reactors series connection are reacted by controlling
Device inlet temperature and each reactor temperature liter realize the control to reaction, wherein intersegmental use air-cooled or water cooling, withdraw reaction
Heat, reaction heat do not efficiently use, and consume a large amount of recirculated cooling water or electric energy, and comparative example 1 does not generate low-pressure steam, embodiment
The quantity of steam generated in 4 is 0.930 ton of steam/1 ton 1,2- epoxy butanes, while the CHP conversion ratios and 1 in embodiment 4,2- rings
Oxygen butane molar selectivity is superior to comparative example 1.
The production technology of epoxy butane proposed by the present invention not only reduces reactor quantity, also reduces energy consumption, while also big
The big molar selectivity for improving CHP conversion ratios and 1,2- epoxy butanes.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications etc.
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (8)
1. one kind 1, the production technology of 2- epoxy butanes, which is characterized in that include the following steps：2 feed pump of logistics is passed through in logistics 2
It is divided into logistics 3 and logistics 4 after supercharging, logistics 4 mixes after preheating with by the logistics 1 after supercharged of 1 feed pump of logistics laggard
Enter calandria type fixed bed reactor, cold shock logistics and process of the logistics 3 as adjustment heat-insulating fixed bed reactors inlet temperature
Enter heat-insulating fixed bed reactors after reaction product mixing after calandria type fixed bed reactor reaction, is fixed by heat-insulating
Logistics after bed reactor reaction, as contains the reaction product of 1,2- epoxy butanes, and the logistics 1 is hydrogen peroxide isopropyl
Benzene or hydrogen peroxide ethylbenzene, logistics 2 are 1- butylene.
2. the production technology of 1,2- epoxy butanes according to claim 1, which is characterized in that the 1- butylene and peroxide
The molar ratio for changing hydrogen isopropylbenzene or hydrogen peroxide ethylbenzene is 6：1~10：1.
3. the production technology of 1,2- epoxy butanes according to claim 1 or 2, which is characterized in that the shell and tube is solid
Ti-SBA-15 catalyst is loaded in fixed bed reactor and heat-insulating fixed bed reactors.
4. the production technology of 1,2- epoxy butanes according to claim 3, which is characterized in that described is calandria type fixed bed
Ti-SBA-15 loaded catalyst mass ratioes are 1 in reactor and heat-insulating fixed bed reactors：1~1：5.
5. the production technology of 1,2- epoxy butanes according to claim 1 or 2, which is characterized in that the shell and tube is solid
Fixed bed reactor reaction pressure is 2.5~4.0MPaG, and reaction temperature is 40 DEG C~130 DEG C.
6. the production technology of 1,2- epoxy butanes according to claim 1 or 2, which is characterized in that the heat-insulating is solid
Fixed bed reactor reaction pressure is 2.5~4.0MPaG, and reaction temperature is 60 DEG C~130 DEG C.
7. the production technology of 1,2- epoxy butanes according to claim 1 or 2, which is characterized in that the shell and tube is solid
Fixed bed reactor shell side top is symmetrically arranged with gas-liquid mixture circulation duct, and gas-liquid mixture circulation duct is connected to drum,
Circulating hot water outlet is provided on drum, circulating hot water outlet is connected to circulating hot water pipeline, circulating hot water pipeline one end and vapour
Packet connection, the other end are solid by the circulating hot water entrance and shell and tube for being symmetricly set on calandria type fixed bed reactor shell side lower part
Fixed bed reactor is connected to.
8. the production technology of 1,2- epoxy butanes according to claim 1, which is characterized in that described is calandria type fixed bed
A reactor outlet logistics part is recycled to calandria type fixed bed reactor entrance, and another part enters heat-insulating fixed bed reaction
Device participates in reaction.
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Cited By (1)
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| CN114478441A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Method, system and application for preparing alkylene oxide |
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