CN104190340B - A kind of micro-tubular reaction unit and utilize this device to prepare the technique of hydrogenated nitrile-butadiene rubber - Google Patents
A kind of micro-tubular reaction unit and utilize this device to prepare the technique of hydrogenated nitrile-butadiene rubber Download PDFInfo
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Abstract
The invention discloses a kind of micro-tubular reaction unit and utilize this device to prepare the technique of hydrogenated nitrile-butadiene rubber, comprising the steam groove that warm-up block I and reaction module II, warm-up block I comprise heat conduction oil groove or sealing and the materail tube be placed in groove; Reaction module II by heat conduction oil groove or sealing steam groove, charging mixing distributor, main reaction materail tube and go out feed mixer and form; Charging mixing distributor, main reaction materail tube are arranged in heat conduction oil groove with going out after feed mixer is connected successively from top to bottom; The material discharging opening of warm-up block is connected with the charging aperture of material feeding mixing distributor.Micro-tubular reaction unit is formed by multiple module assembled, convenient installs and dismounting, can overcome a difficult problem for existing microchannel reaction unit not easy cleaning maintenance.On the other hand the material caliber of this reaction unit is at below 10mm, and adds multiple mixing distributor in connection procedure, remains the high and security advantages of higher of general micro-reaction device mass transfer, heat transfer efficiency.
Description
Technical field
The present invention relates to the preparation field of a kind of microchannel reaction unit, particularly relate to a kind of micro-tubular reaction unit and utilize this device to prepare the technique of hydrogenated nitrile-butadiene rubber.
Background technology
Enter 21 century, micro-reacting tcchnology has become study hotspot new in synthetic chemistry field, is exactly the most significantly the application of microchannel reaction unit.Such as Chinese patent CN101698646A designs and adopts micro passage reaction continous way nitration processes, can efficiently solve the defective workmanship of nitration reaction temperature runaway blast, and the continous way achieving nitrate is produced.The micro-structural of reaction unit inside, microchannel makes micro-reaction device equipment have great specific area, can reach traditional still reaction device hundreds of even thousands of times.Microchannel reaction unit has high mass transfer, rate of heat transfer, can realization response thing moment mixing and efficient heat transfer, compare popular response device to there is reaction condition gentleness, safety and environmental protection, be easy to the advantages such as amplification, and many reactions that cannot realize in popular response device can realize in micro-reaction device.
Along with the continuous aggravation of the problems such as whole world environmental pollution lack of energy, chemical industrial field faces huge Oppertunities and challenges, and the means of chemical reaction of research novel high-efficiency environment friendly economy is extremely urgent.In view of the plurality of advantages problem of microchannel reaction, many scientists further investigate it, and current micro-reaction device is widely used in the research and development of chemical engineering process, and the application in commercially producing is just increasing.Its main application fields comprises organic building-up process, the preparation of micron and nano material and the production of household chemicals, and we believe that micro-reaction device will give play to huge effect in chemical industry.But current micro-reaction device also exists the problem of installing and dismantling inconvenience.
Summary of the invention
The present invention is in order to solve the problems of the technologies described above, a kind of micro-tubular reaction unit is provided and utilizes this device to prepare the technique of hydrogenated nitrile-butadiene rubber, this reaction unit is formed by multiple module assembled, convenient installs and dismounting, can overcome a difficult problem for existing microchannel reaction unit not easy cleaning maintenance.Simultaneously based on the technique preparing hydrogenated nitrile-butadiene rubber of this device, hydrogenated nitrile-butadiene rubber hydrogenation of net product degree prepared by this preparation technology is up to more than 96%, compare the catalytic amount minimizing more than 15% that tank reactor consumes, reaction time shortens more than at least 30 times, significantly reduce energy consumption and production cost, and the continuous prodution of hydrogenated nitrile-butadiene rubber can be realized very easily.Have that structure of reactor is simple, easy to operate, energy consumption is low, the reaction time is short, security is high, without side reaction, the advantage such as environmental pollution is little, technological process is simple and production cost is low.
The present invention is achieved through the following technical solutions:
A kind of micro-tubular reaction unit, comprises warm-up block I and reaction module II, warm-up block I comprise the steam groove of heat conduction oil groove or sealing and be placed in multiple materail tubes of its inside; Reaction module II by heat conduction oil groove or sealing steam groove, charging mixing distributor, main reaction materail tube and go out feed mixer and form; Charging mixing distributor, main reaction materail tube are arranged in the steam groove of heat conduction oil groove or sealing with going out after feed mixer is connected successively from top to bottom; The discharging opening of warm-up block I is connected with the charging aperture of charging mixing distributor.
Each materail tube is corresponding respectively to be comprised for the materail tube charging aperture of material input and the materail tube discharging opening for material outflow; Described charging mixing distributor is provided with multiple discharging opening and multiple charging aperture, each materail tube discharging opening is corresponding with the charging aperture of the charging mixing distributor of reaction module II to be respectively connected; Described main reaction materail tube is rearranged by multiple materail tube; Multiple materail tube is corresponding to materail tube charging aperture and materail tube discharging opening respectively; Go out feed mixer comprise the charging aperture of feed mixer and go out the discharging opening of feed mixer; The discharging opening of charging mixing distributor is connected with multiple materail tube charging apertures of main reaction materail tube; Multiple materail tube discharging openings of main reaction materail tube are connected with the charging aperture going out feed mixer, wherein, the number of the materail tube in main reaction materail tube is identical with the discharging opening number of charging mixing distributor, the discharging opening number of charging mixing distributor is at 2-20, and the length that materail tube often saves is at 4-100m.
The discharging opening number of described charging mixing distributor is at 4 ~ 10, and the length that materail tube often saves is at 10 ~ 50m.
Described materail tube is one or more mixing in blank pipe, interior casting resin pipe and other tubular reactors, materail tube channel diameter 0.01 ~ 10mm.
This device adopts seamless welding to be connected with cutting ferrule, and this device adopts carbon steel, stainless steel, alloy to make.
A Large Copacity charging mixing distributor is provided with between described warm-up block I and reaction module II; Be provided with Large Copacity after reaction module II and go out feed mixer; Large Copacity charging mixing distributor comprises multiple charging aperture and multiple discharging opening; Large Copacity goes out feed mixer and comprises multiple charging aperture and a discharging opening; Charging mixing distributor in reaction module II is a charging aperture and multiple discharging opening; The charging aperture of Large Copacity charging mixing distributor is connected with the discharging opening of warm-up block; Multiple discharging openings of Large Copacity charging mixing distributor are connected with the charging aperture of the charging mixing distributor in the reaction module II after the mutual series connection of multiple parallel connection respectively; Multiple charging apertures that discharging opening in the reaction module II of multiple parallel connection and Large Copacity go out feed mixer are connected, and wherein, the discharging opening number of Large Copacity charging mixing distributor is identical with the number in parallel of reaction module II.
The number of described reaction module II is multiple, and 2 ~ 20 reaction module II are connected in series mutually, the reaction module II connection parallel with one another after 2 ~ 10 series connection.
Go out feed mixer and charging mixing distributor similar, the former charging aperture number is identical with the latter's discharging opening number, and the cavity size of the two and micro-structural identical, difference is that the former only has a discharging opening, and the latter has one or more charging aperture.
Utilize described micro-tubular reaction unit to prepare a technique for hydrogenated nitrile-butadiene rubber, comprise the following steps:
1. first by raw material acrylonitrile-butadiene rubber (NBR), homogeneous catalyst three (triphenylphosphine) radium chloride [RhCl (PPh
3)
3], ligand triphenylphosphine (PPh
3) add in solvent and be mixed with certain density glue, described NBR concentration is 1% ~ 15%, catalyst RhCl (PPh
3)
3be 50 ~ 300ppm with the mass ratio of NBR, part PPh
3be 0.005 ~ 0.2:1 with the mass ratio of NBR;
2. open heating system, make warm-up block I and reaction module II be heated to set temperature;
3. the warm-up block I that the glue prepared and excessive hydrogen are delivered to micro-tubular reaction unit is 1. walked by above-mentioned, glue and hydrogen enter in respective materail tube respectively, be preheating to set temperature in flow process after, flow out via materail tube discharging opening again, the charging mixing distributor entering reaction module II mixes, uniform distribution becomes many parts to enter in multiple materail tubes of main reaction materail tube to react again, the material mixed progressively reacts in main reaction materail tube flow process, reacted material enters out feed mixer and converges and mix, flowed out by the discharging opening going out feed mixer again and enter knockout drum, regulate glue flow velocity at 30 ~ 150L/h, regulate hydrogen flowing quantity to make hydrogen gas pressure at 5 ~ 20MPa, reaction temperature controls at 80 ~ 160 DEG C,
4. above-mentioned reacted product gas after knockout drum is separated flows into hydrogen recycling can from gas-liquid separation upper end, and glue flow in thick products pot via knockout drum bottoms discharging opening;
5. thick product is through Removal of catalyst, solvent evaporated, devolatilization and extruded process, obtains product hydrogenated nitrile-butadiene rubber.
Comprise the following steps:
1. first by raw material acrylonitrile-butadiene rubber (NBR), homogeneous catalyst three (triphenylphosphine) radium chloride [RhCl (PPh
3)
3], ligand triphenylphosphine (PPh
3) add in solvent and be mixed with certain density glue, described NBR concentration is 5% ~ 10%, catalyst RhCl (PPh
3)
3be 175 ~ 300ppm with the mass ratio of NBR, part PPh
3be 0.02 ~ 0.1:1 with the mass ratio of NBR;
2. open heating system, make warm-up block I and reaction module II be heated to set temperature;
3. the warm-up block I that the glue prepared and excessive hydrogen are delivered to micro-tubular reaction unit is 1. walked by above-mentioned, glue and hydrogen enter in respective materail tube respectively, be preheating to set temperature in flow process after, flow out via materail tube discharging opening again, the charging mixing distributor entering reaction module II mixes, uniform distribution becomes many parts to enter in multiple materail tubes of main reaction materail tube to react again, the material mixed progressively reacts in main reaction materail tube flow process, reacted material enters out feed mixer and converges and mix, flowed out by the discharging opening going out feed mixer again and enter knockout drum, regulate glue flow velocity at 90 ~ 150L/h, regulate hydrogen flowing quantity to make hydrogen gas pressure at 8 ~ 13MPa, reaction temperature controls at 100 ~ 140 DEG C,
4. above-mentioned reacted product gas after knockout drum is separated flows into hydrogen recycling can from gas-liquid separation upper end, and glue flow in thick products pot via knockout drum bottoms discharging opening;
5. thick product is through Removal of catalyst, solvent evaporated, devolatilization and extruded process, obtains product hydrogenated nitrile-butadiene rubber.
Compared with prior art, the present invention has following useful technique effect:
Micro-tubular reaction unit provided by the invention is formed by multiple module assembled, convenient installs and dismounting, can overcome a difficult problem for existing microchannel reaction unit not easy cleaning maintenance.According to the corresponding micro-tubular reaction unit of the condition rapid-assembling of required reaction, can also can improve corresponding technological process by rapid Design.On the other hand the material caliber of this reaction unit is at below 10mm, and adds multiple blender in connection procedure, remains the high and security advantages of higher of general micro-reaction device mass transfer, heat transfer efficiency.Based on the continously hydrogen adding production technology of the acrylonitrile-butadiene rubber of a kind of micro-tubular reaction unit of the present invention, the hydrogenated nitrile-butadiene rubber hydrogenation of net product degree of preparation is up to more than 96%, compare the catalytic amount minimizing more than 15% that tank reactor consumes, reaction time shortens more than at least 30 times, significantly reduce energy consumption and production cost, and the continuous prodution of hydrogenated nitrile-butadiene rubber can be realized very easily.Have that structure of reactor is simple, easy to operate, energy consumption is low, the reaction time is short, security is high, without side reaction, the advantage such as environmental pollution is little, technological process is simple and production cost is low.
Accompanying drawing explanation
Fig. 1 is micro-tubular reaction unit structure chart when comprising a reaction module II in the present invention;
Wherein, warm-up block I:A is heat conduction oil groove or steam groove; I
1, I
2, I
3... be each materail tube charging aperture of warm-up block; N1, n2, n3... are materail tube; C
1, C
2, C
3... be each materail tube discharging opening of warm-up block.
Reaction module II:B is heat conduction oil groove or steam groove; D is charging mixing distributor; D1, d2, d3... are the charging aperture of each material of charging mixing distributor; D1, D2, D3... are the discharging opening of charging mixing distributor; R is main reaction materail tube R1, R2, R3...; E1, e2, e3... are the charging aperture of the materail tube of main reaction materail tube; E1, E2, E3... are the discharging opening of the materail tube of main reaction materail tube; F is for going out feed mixer; F1, f2, f3... are for going out feed mixer charging aperture; Fc is for going out feed mixer discharging opening.
Fig. 2 is the micro-tubular reaction unit structure chart using micro-tubular reaction unit of the present invention to prepare hydrogenated nitrile-butadiene rubber; Wherein, I
1for the hydrogen feed mouth of warm-up block I; I
2for the NBR glue charging aperture of warm-up block I; N1 is hydrogen materail tube; N2 is NBR glue materail tube; [D] Large Copacity charging mixing distributor; [F] Large Copacity goes out feed mixer.
Detailed description of the invention
Bromine iodine method is all taked to detect hydrogenated nitrile-butadiene rubber in following instance.
Following embodiment is for further illustrating the present invention, instead of limit the scope of the invention, following examples are the technique based on using the present invention a kind of novel micro-tubular reaction unit to prepare hydrogenated nitrile-butadiene rubber, but those skilled in the art can understand this technique is equally applicable to the catalytic hydrogenation of other unsaturated copolymers and numerous association areas of other similar multi-component masses mixing mass transfers and reaction.
See Fig. 1 to Fig. 2, a kind of micro-tubular reaction unit, comprise warm-up block I and reaction module II, see Fig. 1, warm-up block I comprises the steam groove A of heat conduction oil groove or sealing and is placed in multiple materail tubes of groove inside, wherein heat conduction oil groove can blow-by (sealing of steam groove), and heat conduction oil groove inside is for preheating/cooling medium flowing; Reaction module II by heat conduction oil groove or sealing steam groove B, charging mixing distributor D, main reaction materail tube R and go out feed mixer F and form, wherein heat conduction oil groove can flow for heating/cooling medium blow-by (sealing of steam groove) inside, charging mixing distributor D, main reaction materail tube R are arranged in the steam groove B of heat conduction oil groove or sealing with going out after feed mixer F is connected successively from top to bottom, and the discharging opening of warm-up block I is connected with the charging aperture of charging mixing distributor D.
Concrete, each materail tube is the corresponding materail tube charging aperture I comprised for material input respectively
1, I
2, I
3... and for the materail tube discharging opening C that material flows out
1, C
2, C
3described charging mixing distributor D is provided with multiple discharging opening D1, D2, D3 ... with multiple charging aperture d1, d2, d3 ..., each materail tube discharging opening C
1, C
2, C
3respectively with the charging aperture d1 of the charging mixing distributor D of reaction module II, d2, d3 ... corresponding connection; Described main reaction materail tube R is by multiple materail tube R1, R2, R3 ... rearrange, multiple materail tube is corresponding to materail tube charging aperture e1, e2 respectively, e3 ... with materail tube discharging opening E1, E2, E3 ..., go out the charging aperture f1 that feed mixer F comprises feed mixer F, f2, f3 ... with the discharging opening F going out feed mixer F
c, the discharging opening D1 of charging mixing distributor D, D2, D3 ... with multiple materail tube charging aperture e1 of main reaction materail tube R, e2, e3 ... be connected; Multiple materail tube discharging opening E1 of main reaction materail tube R, E2, E3 ... with the charging aperture f1 going out feed mixer F, f2, f3 ... be connected, wherein, the number of the materail tube in main reaction materail tube R and the discharging opening D1 of charging mixing distributor D, D2, D3 ... number is identical, the discharging opening number of charging mixing distributor D is at 2-20, and the length that materail tube often saves is at 4-100m.
The discharging opening number optimal selection of described charging mixing distributor D at 4 ~ 10, materail tube R1 in reaction module II, the effect length reaction efficiency that R2, R3... often save.Materail tube length is too short on the one hand, and equipment is installed inconvenient, cost improves; Materail tube length is oversize on the other hand, and the efficiency mixed between various material reduces, and then causes reaction efficiency to reduce, and the length that materail tube often saves is at 10 ~ 50m.
Described materail tube is one or more mixing in blank pipe, interior casting resin pipe and other tubular reactors, materail tube channel diameter 0.01 ~ 10mm.
This device adopts seamless welding to be connected with cutting ferrule, and this device can adopt carbon steel, stainless steel, alloy etc. to make according to the reaction type occurred concrete in equipment; Described micro-tubular reaction unit, blender and materail tube material selection stainless steel or alloy.
For improving reaction efficiency and increasing production scale, a Large Copacity charging mixing distributor [D] is provided with between described warm-up block I and reaction module II, be provided with Large Copacity after reaction module II and go out feed mixer [F], Large Copacity charging mixing distributor [D] comprises multiple charging aperture and multiple discharging opening, Large Copacity goes out feed mixer [F] and comprises multiple charging aperture and a discharging opening, charging mixing distributor D in reaction module II is a charging aperture and multiple discharging opening, the charging aperture of Large Copacity charging mixing distributor [D] is connected with the discharging opening of warm-up block, multiple discharging openings of Large Copacity charging mixing distributor [D] are connected with the charging aperture of the charging mixing distributor D in the reaction module II after the mutual series connection of multiple parallel connection respectively, multiple charging apertures that discharging opening in the reaction module II of multiple parallel connection and Large Copacity go out feed mixer [F] are connected, wherein, the discharging opening number of Large Copacity charging mixing distributor [F] is identical with the number in parallel of reaction module II.Wherein, feed mixer F and charging mixing distributor D similar is gone out in same reaction module II, the former charging aperture number is identical with the latter's discharging opening number, and the former discharging opening number and the charging aperture number of the latter are one, and the cavity size of the two and micro-structural identical.
Described micro-tubular reaction unit prepares the technique of hydrogenated nitrile-butadiene rubber, the number of described reaction module II is multiple, 2 ~ 20 reaction module II are connected in series mutually, reaction module II connection parallel with one another after 2 ~ 10 series connection, by connecting, multiple reaction module II improves reaction efficiency, and the reaction module II number of optimal selection series connection is 6 ~ 15.
Further, described micro-tubular reaction unit prepares the technique of hydrogenated nitrile-butadiene rubber, expands production capacity by the multiple reaction module II of parallel connection, and the reaction module II number of single metering pump optimal selection parallel connection is 3 ~ 6, and production capacity can reach 600L/h.Optimum hydrogen gas pressure is 6 ~ 13MPa.
See Fig. 2, a kind of technique utilizing described micro-tubular reaction unit to prepare hydrogenated nitrile-butadiene rubber, comprises the following steps:
1. first by raw material acrylonitrile-butadiene rubber (NBR), homogeneous catalyst three (triphenylphosphine) radium chloride [RhCl (PPh
3)
3], ligand triphenylphosphine (PPh
3) add in solvent and be mixed with certain density glue, described NBR concentration is 8%, catalyst RhCl (PPh
3)
3be 300ppm with the mass ratio of NBR, part PPh
3be 0.005:1 with the mass ratio of NBR;
2. open heating system, make warm-up block I and reaction module II be heated to temperature 100 DEG C;
3. the warm-up block I that the glue prepared and excessive hydrogen are delivered to micro-tubular reaction unit is 1. walked by above-mentioned, glue and hydrogen enter in respective materail tube respectively, be preheating to set temperature in flow process after, flow out via materail tube discharging opening again, the charging mixing distributor entering reaction module II mixes, uniform distribution becomes many parts to enter in multiple materail tubes of main reaction materail tube to react again, the material mixed progressively reacts in the flow process of main reaction materail tube, reacted material enters out feed mixer and converges and mix, again by the discharging opening F going out feed mixer
coutflow enters knockout drum, regulate glue flow velocity at 90L/h, regulate hydrogen flowing quantity to make hydrogen gas pressure at 17.5MPa, reaction temperature controls at 120 DEG C,
4. above-mentioned reacted product is after knockout drum is separated, and gas flows into hydrogen recycling can from gas-liquid separation upper end, and glue flow in thick products pot via knockout drum bottoms discharging opening;
5. thick product is through Removal of catalyst, solvent evaporated, devolatilization and extruded process, obtains product hydrogenated nitrile-butadiene rubber.
Utilize described micro-tubular reaction unit to prepare a technique for hydrogenated nitrile-butadiene rubber, comprise the following steps:
1. first by raw material acrylonitrile-butadiene rubber (NBR), homogeneous catalyst three (triphenylphosphine) radium chloride [RhCl (PPh
3)
3], ligand triphenylphosphine (PPh
3) add in solvent and be mixed with certain density glue, described NBR concentration is 15%, catalyst RhCl (PPh
3)
3be 50ppm with the mass ratio of NBR, part PPh
3be 0.1:1 with the mass ratio of NBR;
2. open heating system, make warm-up block I and reaction module II be heated to temperature 100 DEG C;
3. the warm-up block I that the glue prepared and excessive hydrogen are delivered to micro-tubular reaction unit is 1. walked by above-mentioned, after glue and hydrogen are preheating to set temperature in flow process, the charging mixing distributor entering reaction module II again mixes, uniform distribution becomes many parts to enter main reaction materail tube to react again, the material mixed progressively reacts in the flow process of main reaction materail tube, reacted material enters out feed mixer and converges and mix, then enters knockout drum by the discharging opening outflow going out feed mixer; Regulate glue flow velocity at 150L/h, regulate hydrogen flowing quantity to make hydrogen gas pressure at 20MPa, reaction temperature controls at 160 DEG C;
4. above-mentioned product is after knockout drum is separated, and gas flows into hydrogen recycling can from gas-liquid separation upper end, and glue flow in thick products pot via knockout drum bottoms discharging opening;
5. thick product is through Removal of catalyst, solvent evaporated, devolatilization and extruded process, obtains product hydrogenated nitrile-butadiene rubber.
Utilize described micro-tubular reaction unit to prepare a technique for hydrogenated nitrile-butadiene rubber, comprise the following steps:
1. first by raw material acrylonitrile-butadiene rubber (NBR), homogeneous catalyst three (triphenylphosphine) radium chloride [RhCl (PPh3) 3], ligand triphenylphosphine (PPh3) adds in solvent and is mixed with certain density glue, described NBR concentration is 1%, catalyst RhCl (PPh3) 3 is 175ppm with the mass ratio of NBR, and the mass ratio of part PPh3 and NBR is 0.2:1;
2. open heating system, make warm-up block I and reaction module II be heated to temperature 100 DEG C;
3. the warm-up block I that the glue prepared and excessive hydrogen are delivered to micro-tubular reaction unit is 1. walked by above-mentioned, after glue and hydrogen are preheating to set temperature in flow process, the charging mixing distributor entering reaction module II again mixes, uniform distribution becomes many parts to enter main reaction materail tube to react again, the material mixed progressively reacts in the flow process of main reaction materail tube, reacted material enters out feed mixer and converges and mix, then enters knockout drum by the discharging opening outflow going out feed mixer; Regulate glue flow velocity at 30L/h, regulate hydrogen flowing quantity to make hydrogen gas pressure at 5MPa, reaction temperature controls at 80 DEG C;
4. above-mentioned product is after knockout drum is separated, and gas flows into hydrogen recycling can from gas-liquid separation upper end, and glue flow in thick products pot via knockout drum bottoms discharging opening;
5. thick product is through Removal of catalyst, solvent evaporated, devolatilization and extruded process, obtains product hydrogenated nitrile-butadiene rubber.
Embodiment 1
The microchannel reaction unit selected has following parameter: adopt a reaction module II to react, the charging aperture number of feed liquor mixing distributor D is 2, and discharging opening number is 8, and materail tube selects internal diameter to be the empty stainless steel tube of 2mm, often saving materail tube length is 40m, and concrete operation step is as follows:
1. first by raw material acrylonitrile-butadiene rubber (NBR), homogeneous catalyst three (triphenylphosphine) radium chloride [RhCl (PPh3) 3], ligand triphenylphosphine (PPh3) adds in solvent and is mixed with certain density glue, wherein said NBR concentration is 6%, catalyst RhCl (PPh3) 3 is 200ppm with the mass ratio of NBR, and the mass ratio of part PPh3 and NBR is 0.02:1.
2. open heating system, make warm-up block I and reaction module II be heated to set temperature 100 DEG C;
3. the glue for preparing 1. is walked by above-mentioned the with the flow velocity of 100L/h metering transport pump to the charging aperture I2 of pre-heating module I, high pressure hydrogen enters from another charging aperture I1, after glue and hydrogen are preheating to set temperature in flow process, then enter charging mixing distributor D to mix, average mark is made into many parts and enters main reaction materail tube R and react again, the material mixed progressively reacts in the flow process of main reaction materail tube R, reacted material enters out feed mixer F and converges and mix, flowed out by the discharging opening Fc going out feed mixer F again and enter knockout drum.Regulate hydrogen flowing quantity to make hydrogen gas pressure at more than 8MPa, reaction temperature controls at 100 DEG C, and glue conveying flow rate set is 100L/h;
4. above-mentioned product is after knockout drum is separated, and gas flows into hydrogen recycling can from gas-liquid separation upper end, and product glue flow in thick products pot via knockout drum bottoms discharging opening;
5. thick product can obtain final product hydrogenated nitrile-butadiene rubber through Removal of catalyst, solvent evaporated, devolatilization and the step such as extruded.Adopt bromine iodine method to detect product, degree of hydrogenation is 10.6%.Concrete reaction condition and the results are shown in Table 1.
Embodiment 2
In embodiment 1, then 1 the reaction module II that connects reacts, and adopt bromine iodine method to detect product, degree of hydrogenation is 30.4%.Concrete reaction condition and the results are shown in Table 1.
Embodiment 3
In embodiment 1, then 3 the reaction module II that connect react, and adopt bromine iodine method to detect product, degree of hydrogenation is 45.3%.Concrete reaction condition and the results are shown in Table 1.
Embodiment 4
In embodiment 1, then 5 the reaction module II that connect react, and adopt bromine iodine method to detect product, degree of hydrogenation is 77.0%.Concrete reaction condition and the results are shown in Table 1.
Embodiment 5
In embodiment 1, then 7 the reaction module II that connect react, and adopt bromine iodine method to detect product, degree of hydrogenation is 88.1%.Concrete reaction condition and the results are shown in Table 1.
Embodiment 6
In embodiment 1, then 9 the reaction module II that connect react, and adopt bromine iodine method to detect product, degree of hydrogenation is 96.1%.Concrete reaction condition and the results are shown in Table 1.
Table 1 uses micro-tubular reaction unit of the present invention to prepare process conditions and the product information of hydrogenated nitrile-butadiene rubber
In table 1: catalyst concn by the mass ratio of rhodium ion and dry glue, unit ppm (1,000,000/)
The reaction condition of comparative example 1,2,3,4,5,6 finds, under the condition that other conditions are all identical, the reaction module II number of micro-tubular reaction unit series connection is more, and materail tube total length is longer, and the air inflow of hydrogen can be less.This is because the micro-tubular reaction unit non-closed reaction unit that is a kind of continuous print, materail tube total length is longer, and under the condition that inlet pressure is equal, the gradient of pressure drop is less, and hydrogen is more difficult to get access in materail tube.The degree of hydrogenation of comparative example 1,2,3,4,5,6 product found that, the reaction module II number of micro-tubular reaction unit series connection is more, and materail tube total length is longer, and the time that material reacts in materail tube is longer, and degree of hydrogenation is higher.
Embodiment 7
In embodiment 6, the addition of catalyst is changed to 120ppm, and adopt bromine iodine method to detect product, degree of hydrogenation is 74.4%.Concrete reaction condition and the results are shown in Table 1.
Embodiment 8
In embodiment 1, the addition of catalyst is changed to 150ppm, and adopt bromine iodine method to detect product, degree of hydrogenation is 85.7%.Concrete reaction condition and the results are shown in Table 1.
Embodiment 9
In embodiment 1, the addition of catalyst is changed to 170ppm, and adopt bromine iodine method to detect product, degree of hydrogenation is 95.2%.Concrete reaction condition and the results are shown in Table 1.
Comparative example 6,7,8,9 found that, increases the concentration of catalyst and can improve reaction efficiency, but after catalyst concn is greater than 170ppm, then increasing the amount of catalyst, the amplitude that hydrogenation of net product degree improves obviously reduces.
In order to compare the hydrogenation effect of micro-tubular reaction unit of the present invention and still reaction device, first use still reaction device to prepare the HNBR rubber (see table 2) of a series of different model, the general step that still reaction device prepares hydrogenated nitrile-butadiene rubber is as follows:
First in 100L autoclave, add the acrylonitrile-butadiene rubber (NBR) that cumulative volume is 70L, the chlorobenzene solution of rhodium catalyst and ligand triphenylphosphine (PPh3), wherein the concentration of NBR is 6%, ligand concentration is 2% (mass ratio by dry glue), in reactor, hydrogen is filled with again after nitrogen displacement, pressure in still is made to maintain more than 8MPa, open and heat and stir, after solution temperature in still reaches 100 DEG C, (need the time to be about 45min), again Keep agitation reaction 6h (if in course of reaction in still pressure lower than 8MPa, hydrogen make-up immediately), the hydrogenated nitrile-butadiene rubber hydrogenation of net product degree obtained sees the following form 2.
Comparison sheet 1, found that of table 2, embodiment 9 and production code member 3 are when raw material model, gelatin concentration, catalyst concn, ligand concentration and reaction temperature etc. are identical, the catalytic amount using micro-tubular reaction unit of the present invention to consume than still reaction device reduces 15%, identical degree of hydrogenation (95%) can be reached, and the former reaction time shortens more than 30 times than the latter, energy consumption reduces greatly.
The technique using micro-tubular reaction unit of the present invention to prepare hydrogenated nitrile-butadiene rubber can be continuously produced and passes through mode rapid expansion production scale in parallel, and can not extend the production time.A kind of novel micro passage reaction of current the present invention and use this equipment to prepare the technique of hydrogenated nitrile-butadiene rubber also in the further optimizing phase, what we believed passes through constantly to make great efforts, the production cost preparing hydrogenated nitrile-butadiene rubber can be made significantly to reduce, and production security increases substantially.
The HNBR product information list that table 2 uses 100L tank reactor to prepare
In table 2: catalyst concn by the mass ratio of rhodium ion and dry glue, unit ppm (1,000,000/)
Hydrogenated nitrile-butadiene rubber hydrogenation of net product degree prepared by this technique is up to more than 96%, and compare tank reactor catalyst consumption amount and reduce more than 15%, the reaction time shortens more than at least 30 times, and can realize the continuous prodution of hydrogenation very easily.
In addition, this device can also be applied to the numerous association areas mixing mass transfer and reaction between other similar fluids, and this technique is equally applicable to the catalytic hydrogenation of other unsaturated copolymers and numerous association areas of other similar multicomponent mixing mass transfers and reaction.
The present invention devises a kind of novel micro-tubular reaction unit, and this reaction unit is formed by multiple module assembled, convenient installs and dismounting, can overcome a difficult problem for existing microchannel reaction unit not easy cleaning maintenance.According to the corresponding micro-tubular reaction unit of the condition rapid-assembling of required reaction, can also can improve corresponding technological process by rapid Design.On the other hand the material caliber of this reaction unit is at below 10mm, and adds multiple blender in connection procedure, remains the high and security advantages of higher of general micro-reaction device mass transfer, heat transfer efficiency.Based on the continously hydrogen adding production technology of the acrylonitrile-butadiene rubber of a kind of novel micro-tubular reaction unit of the present invention, the hydrogenated nitrile-butadiene rubber hydrogenation of net product degree of preparation is up to more than 96%, compare the catalytic amount minimizing more than 15% that tank reactor consumes, reaction time shortens more than at least 30 times, significantly reduce energy consumption and production cost, and the continuous prodution of hydrogenated nitrile-butadiene rubber can be realized very easily.Have that reaction unit structure is simple, easy to operate, energy consumption is low, the reaction time is short, security is high, without side reaction, the advantage such as environmental pollution is little, technological process is simple and production cost is low.
More than show and describe general principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and description just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (9)
1. a micro-tubular reaction unit, is characterized in that, comprises warm-up block I and reaction module II, warm-up block I comprise the steam groove (A) of heat conduction oil groove or sealing and be placed in multiple materail tubes of its inside; Reaction module II by heat conduction oil groove or sealing steam groove (B), charging mixing distributor (D), main reaction materail tube (R) and go out feed mixer (F) and form; Charging mixing distributor (D), main reaction materail tube (R) are arranged in the steam groove (B) of heat conduction oil groove or sealing with going out after feed mixer (F) is connected successively from top to bottom; The discharging opening of warm-up block I is connected with the charging aperture of charging mixing distributor (D).
2. micro-tubular reaction unit according to claim 1, is characterized in that, the materail tube in each warm-up block is the corresponding materail tube charging aperture (I comprised for material input respectively
1, I
2, I
3...) and for material flow out materail tube discharging opening (C
1, C
2, C
3); Described charging mixing distributor (D) is provided with multiple discharging opening (D1, D2, D3 ...) and multiple charging aperture (d1, d2, d3 ...), each materail tube discharging opening (C
1, C
2, C
3) respectively with charging aperture (d1, d2, the d3 of the charging mixing distributor (D) of reaction module II ...) correspondence is connected; Described main reaction materail tube (R) is by multiple materail tube (R1, R2, R3 ...) rearrange; The materail tube of multiple main reaction thing materail tube is corresponding to materail tube charging aperture (e1, e2, e3 respectively ...) and materail tube discharging opening (E1, E2, E3 ...); Go out charging aperture (f1, f2, f3 that feed mixer (F) comprises feed mixer (F) ...) and go out the discharging opening (F of feed mixer (F)
c); Discharging opening (D1, D2, the D3 of charging mixing distributor (D) ...) with multiple materail tube charging aperture (e1, e2, the e3 of main reaction materail tube (R) ...) be connected; Multiple materail tube discharging opening (E1 of main reaction materail tube (R), E2, E3 ...) with go out the charging aperture (f1 of feed mixer (F), f2, f3 ...) be connected, wherein, the number of the materail tube in main reaction materail tube (R) and the discharging opening (D1 of charging mixing distributor (D), D2, D3 ...) number is identical, the discharging opening number of charging mixing distributor (D) is at 2-20, and the length often saved with the materail tube of main reaction thing materail tube in warm-up block is at 4-100m.
3. micro-tubular reaction unit according to claim 2, is characterized in that, the discharging opening number of described charging mixing distributor (D) is at 4 ~ 10, and the length often saved with the materail tube of main reaction thing materail tube in warm-up block is at 10 ~ 50m.
4. micro-tubular reaction unit according to claim 2, is characterized in that, described materail tube is one or more mixing in blank pipe, interior casting resin pipe and other tubular reactors, materail tube channel diameter 0.01 ~ 10mm.
5. micro-tubular reaction unit according to claim 1, is characterized in that, this device adopts seamless welding to be connected with cutting ferrule.
6. micro-tubular reaction unit according to claim 1, is characterized in that, is provided with a Large Copacity charging mixing distributor between described warm-up block I and reaction module II; Be provided with Large Copacity after reaction module II and go out feed mixer; Large Copacity charging mixing distributor comprises multiple charging aperture and multiple discharging opening; Large Copacity goes out feed mixer and comprises multiple charging aperture and a discharging opening, and the charging mixing distributor (D) in reaction module II is a charging aperture and multiple discharging opening; The charging aperture of Large Copacity charging mixing distributor is connected with the discharging opening of warm-up block; Multiple discharging openings of Large Copacity charging mixing distributor are connected with the charging aperture of the charging mixing distributor (D) in the reaction module II after the mutual series connection of multiple parallel connection respectively; Multiple charging apertures that discharging opening in the reaction module II of multiple parallel connection and Large Copacity go out feed mixer are connected, and wherein, the discharging opening number of Large Copacity charging mixing distributor is identical with the number in parallel of reaction module II.
7. micro-tubular reaction unit according to claim 1, it is characterized in that, go out feed mixer (F) and charging mixing distributor (D) similar, the former charging aperture number is identical with the latter's discharging opening number, and the cavity size of the two and micro-structural identical, difference is that the former only has a discharging opening, and the latter has one or more charging aperture.
8. utilize the technique preparing hydrogenated nitrile-butadiene rubber based on the micro-tubular reaction unit described in claim 1-5 or 7 any one, it is characterized in that, comprise the following steps:
1. first by raw material acrylonitrile-butadiene rubber (NBR), homogeneous catalyst three (triphenylphosphine) radium chloride [RhCl (PPh
3)
3], ligand triphenylphosphine (PPh
3) add in solvent and be mixed with certain density glue, described NBR concentration is 1% ~ 15%, catalyst RhCl (PPh
3)
3be 50 ~ 300ppm with the mass ratio of NBR, part PPh
3be 0.005 ~ 0.2:1 with the mass ratio of NBR;
2. open heating system, make warm-up block I and reaction module II be heated to set temperature;
3. the warm-up block I that the glue prepared and excessive hydrogen are delivered to micro-tubular reaction unit is 1. walked by above-mentioned, glue and hydrogen enter in the materail tube in respective warm-up block respectively, be preheating to set temperature in flow process after, flow out via materail tube discharging opening again, the charging mixing distributor (D) entering reaction module II mixes, uniform distribution becomes many parts to enter in multiple materail tubes of main reaction materail tube (R) to react again, the material mixed progressively reacts in main reaction materail tube (R) flow process, reacted material enters out feed mixer (F) and converges and mix, again by the discharging opening (F going out feed mixer (F)
c) flow out enter knockout drum, regulate glue flow velocity at 30 ~ 150L/h, regulate hydrogen flowing quantity to make hydrogen gas pressure at 5 ~ 20MPa, reaction temperature controls at 80 ~ 160 DEG C,
4. above-mentioned reacted product gas after knockout drum is separated flows into hydrogen recycling can from gas-liquid separation upper end, and glue flow in thick products pot via knockout drum bottoms discharging opening;
5. thick product is through Removal of catalyst, solvent evaporated, devolatilization and extruded process, obtains product hydrogenated nitrile-butadiene rubber.
9. the technique utilizing micro-tubular reaction unit to prepare hydrogenated nitrile-butadiene rubber according to claim 8, is characterized in that, comprise the following steps:
1. first by raw material acrylonitrile-butadiene rubber (NBR), homogeneous catalyst three (triphenylphosphine) radium chloride [RhCl (PPh
3)
3], ligand triphenylphosphine (PPh
3) add in solvent and be mixed with certain density glue, described NBR concentration is 5% ~ 10%, catalyst RhCl (PPh
3)
3be 175 ~ 300ppm with the mass ratio of NBR, part PPh
3be 0.02 ~ 0.1:1 with the mass ratio of NBR;
2. open heating system, make warm-up block I and reaction module II be heated to set temperature;
3. the warm-up block I that the glue prepared and excessive hydrogen are delivered to micro-tubular reaction unit is 1. walked by above-mentioned, glue and hydrogen enter in the materail tube in respective warm-up block respectively, be preheating to set temperature in flow process after, flow out via materail tube discharging opening again, the charging mixing distributor (D) entering reaction module II mixes, uniform distribution becomes many parts to enter in multiple materail tubes of main reaction materail tube (R) to react again, the material mixed progressively reacts in main reaction materail tube (R) flow process, reacted material enters out feed mixer (F) and converges and mix, again by the discharging opening (F going out feed mixer (F)
c) flow out enter knockout drum, regulate glue flow velocity at 90 ~ 150L/h, regulate hydrogen flowing quantity to make hydrogen gas pressure at 8 ~ 13MPa, reaction temperature controls at 100 ~ 140 DEG C,
4. above-mentioned reacted product gas after knockout drum is separated flows into hydrogen recycling can from gas-liquid separation upper end, and glue flow in thick products pot via knockout drum bottoms discharging opening;
5. thick product is through Removal of catalyst, solvent evaporated, devolatilization and extruded process, obtains product hydrogenated nitrile-butadiene rubber.
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|---|---|---|---|
| CN201410436581.3A CN104190340B (en) | 2014-08-29 | 2014-08-29 | A kind of micro-tubular reaction unit and utilize this device to prepare the technique of hydrogenated nitrile-butadiene rubber |
| PCT/CN2015/071415 WO2016029644A1 (en) | 2014-08-29 | 2015-01-23 | Micro-tube reaction device and process for preparing hydrogenated nitrile rubber by using device |
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|---|---|---|---|
| CN201410436581.3A CN104190340B (en) | 2014-08-29 | 2014-08-29 | A kind of micro-tubular reaction unit and utilize this device to prepare the technique of hydrogenated nitrile-butadiene rubber |
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| CN104190340B true CN104190340B (en) | 2016-04-06 |
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| CN104190340B (en) * | 2014-08-29 | 2016-04-06 | 高剑峰 | A kind of micro-tubular reaction unit and utilize this device to prepare the technique of hydrogenated nitrile-butadiene rubber |
| CN107335395B (en) * | 2017-09-05 | 2023-11-03 | 山东豪迈化工技术有限公司 | microreactor |
| CN112142883B (en) * | 2019-06-28 | 2022-06-07 | 沈阳化工研究院有限公司 | Continuous hydrogenation method and device for conjugated diene polymer |
| CN113813898B (en) * | 2021-10-22 | 2022-10-28 | 西安交通大学 | Combined supercritical hydrothermal synthesis microchannel reactor |
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| EP1297889A2 (en) * | 2000-03-07 | 2003-04-02 | Symyx Technologies, Inc. | Parallel flow process optimization reactor |
| CN1985175A (en) * | 2004-07-14 | 2007-06-20 | 株式会社荏原制作所 | Microchannel chip reaction control system, micro total reaction system including the control system, and micro total analysis system |
| CN101443111A (en) * | 2006-04-25 | 2009-05-27 | 维罗西股份有限公司 | Flow distribution channels to control flow in process channels |
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| EP1265700B1 (en) * | 2000-03-07 | 2005-01-19 | Symyx Technologies, Inc. | Parallel flow process optimization reactor |
| US7294734B2 (en) * | 2003-05-02 | 2007-11-13 | Velocys, Inc. | Process for converting a hydrocarbon to an oxygenate or a nitrile |
| US7422910B2 (en) * | 2003-10-27 | 2008-09-09 | Velocys | Manifold designs, and flow control in multichannel microchannel devices |
| WO2006031058A1 (en) * | 2004-09-13 | 2006-03-23 | Spec Co., Ltd | Micro channel reactor |
| CN102432471B (en) * | 2011-11-07 | 2013-12-18 | 常州大学 | Method for undergoing chlorobenzene nitration reaction by using micro-channel reactor |
| CN102875322B (en) * | 2012-10-15 | 2014-07-09 | 常州大学 | Method for preparing 2-bromo-2-methylpropane by brominating tert-butyl alcohol through microchannel reactor |
| CN103911194B (en) * | 2013-01-04 | 2016-04-20 | 高剑峰 | composite diesel cetane number improver and production technique thereof |
| CN103333290B (en) * | 2013-07-23 | 2015-09-30 | 蒲城瑞鹰新材料科技有限公司 | A kind of micro passage reaction continuous production processes of hydrogenated nitrile-butadiene rubber |
| CN104190340B (en) * | 2014-08-29 | 2016-04-06 | 高剑峰 | A kind of micro-tubular reaction unit and utilize this device to prepare the technique of hydrogenated nitrile-butadiene rubber |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1297889A2 (en) * | 2000-03-07 | 2003-04-02 | Symyx Technologies, Inc. | Parallel flow process optimization reactor |
| CN1985175A (en) * | 2004-07-14 | 2007-06-20 | 株式会社荏原制作所 | Microchannel chip reaction control system, micro total reaction system including the control system, and micro total analysis system |
| CN101443111A (en) * | 2006-04-25 | 2009-05-27 | 维罗西股份有限公司 | Flow distribution channels to control flow in process channels |
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