CN103254056B - A kind of vitamin K 3preparation method and device - Google Patents
A kind of vitamin K 3preparation method and device Download PDFInfo
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- CN103254056B CN103254056B CN201310135494.XA CN201310135494A CN103254056B CN 103254056 B CN103254056 B CN 103254056B CN 201310135494 A CN201310135494 A CN 201310135494A CN 103254056 B CN103254056 B CN 103254056B
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Abstract
The invention provides a kind of vitamin K
3preparation method and device.Method comprises beta-methylnaphthalene stream, oxide water solution stream and cycling stream combination cooling forming reactions liquid stream, continues reaction solution stream cooling reaction is formed to crude product stream and be separated vitamin K from crude product stream
3; Wherein part crude product stream reenters reaction solution stream as cycling stream; Oxide water solution stream comprises sodium dichromate 99 and sulfuric acid, CrO
3content is 200 ~ 350g/L, and sulfuric acid content is 400 ~ 550g/L, and the throughput ratio of oxide water solution stream and beta-methylnaphthalene stream is 7 ~ 11:1, and the throughput ratio of beta-methylnaphthalene and reaction solution stream is 1:900 ~ 1300; During cooling reaction, temperature controls at 55 ~ 65 DEG C.Device comprises mixing tank, tubulation retort, separating-purifying parts, temperature-controlled member and flow control component.The invention solves existing beta-methylnaphthalene and prepare vitamin K
3process oxidizes process is difficult to control thus affects the problem of transformation efficiency.
Description
Technical field
The invention belongs to chemical field, relate to a kind of vitamin K
3preparation method, still further provides one and prepare vitamin K
3device.
Background technology
β-vitamin k4 (vitamin K
3) synthesis technology, at present domestic all employings autoclave intermittent oxidation beta-methylnaphthalene production line, due to this oxidizing reaction release amount of heat, difficult control of temperature, must adopt refrigerating fulid to carry out heat exchange.The limitation that reaction conditions controls, causes product yield low, and between batch, quality is unstable, and oxidation solution consumption is large.
The reaction process that the oxidation of raw material beta-methylnaphthalene generates β-vitamin k4 easily produces peroxidation phenomenon and the yield of product is reduced, the key of reaction process is the control of oxidizing condition, comprise oxidation solution concentration, beta-methylnaphthalene concentration, mixed effect, temperature of reaction, reaction times etc., all these conditions all have a direct impact the quality of β-vitamin k4 and yield.Beta-methylnaphthalene oxidation can occur on aromatic ring and also can occur in pendant methyl.β-vitamin k4,6-vitamin k4, MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride, carbonic acid gas and water is generated when aromatic ring occurs oxidizing reaction, pendant methyl generation oxidizing reaction then methanol, formaldehyde, formic acid, beta-methylnaphthalene oxidation products changes with oxidizing condition.During intermittent oxidation beta-methylnaphthalene initial beta-methylnaphthalene and oxidation solution concentration high, thermal discharge is large, reaction is violent, in order to control speed of response, prevent the generation of by product, superoxide, General reactions in advance temperature controls at 35 ~ 45 DEG C, now need to use the refrigerating fulid of about-20 DEG C to lower the temperature, because still jacket heat transfer is poor, high β-the vitamin k4 of generation that can make of local temperature produces peroxidation phenomenon, peroxidation consumes oxidation solution and that reaction later stage beta-methylnaphthalene is failed is all oxidized, affects the quality of β-vitamin k4, yield; Along with the carrying out of reaction, beta-methylnaphthalene and oxidation solution concentration reduce, in order to beta-methylnaphthalene oxidation needs to improve temperature of reaction to 55 ~ 65 DEG C completely, if use early stage the cooling of refrigerating fulid temperature control improper, can only pass into steam at still chuck when oxidizing reaction thermal discharge is not enough to make temperature of reaction increase impels temperature of reaction to rise, and energy consumption is higher; The refrigerating fulid passing into about-20 DEG C at still chuck after reaction terminates is cooled to 25 ~ 35 DEG C of dischargings.Quality product fluctuates, process operation is loaded down with trivial details, temperature controls complexity, production efficiency is low.
Summary of the invention
Technical problem to be solved by this invention is that vitamin K is prepared in beta-methylnaphthalene oxidation
3technique, oxidation course is difficult to control, thus affects vitamin K
3transformation efficiency, and a kind of vitamin K is proposed
3preparation method.
A kind of vitamin K of the present invention
3preparation method, comprising:
A. by beta-methylnaphthalene stream, oxide water solution stream and cycling stream combination cooling forming reactions liquid stream;
B. continue to form crude product stream to reaction solution stream cooling reaction;
C. from crude product stream, vitamin K is separated
3;
Part crude product stream in described b step is reused for a step as cycling stream; In a step, oxide water solution stream comprises sodium dichromate 99 and sulfuric acid, CrO
3content is 200 ~ 350g/L, and sulfuric acid content is 400 ~ 550g/L, and the throughput ratio of oxide water solution stream and beta-methylnaphthalene stream is 7 ~ 11:1, and the throughput ratio of beta-methylnaphthalene and reaction solution stream is 1:900-1300; The reaction fluid temperature of described b step controls at 55 ~ 65 DEG C.
The present invention wishes at vitamin K
3preparation process in try not the phenomenon that occurs that local reaction is overheated, because local reaction is overheated make vitamin K by inevasible
3the by product of preparation feedback increases, and it is generally acknowledged, the too high local reaction that can cause of local reaction relative concentration is overheated.The present invention also wishes that the optimum concn that can be easy to the concentration of reactant is designed with the present invention is carried out, and such concentration not only can delay vitamin K
3the exotherm rate of preparation feedback, and guarantee that reaction is carried out at a suitable temperature, and obtain reaction yield large as far as possible.
Usually can eliminate the too high phenomenon of local reaction relative concentration by optimizing alr mode as far as possible, the kinetic energy of stirring itself passes to reactant, and improve the probability carrying out mutual effective collision between reactant, make to be swift in response and carry out, discharging a large amount of heats simultaneously and impel temperature of reaction to raise rapidly, cannot guaranteeing that reaction is to being conducive to vitamin K
3the direction generated is carried out.
The present invention finds to solve the relatively too high problem of reactant partial concn with the form of reactant limit coronite flowing cooling (cooling reaction), and the concentration of beta-methylnaphthalene preferably maintains a lower level, the temperature cooling reaction is maintained and is conducive to vitamin K
3the scope generated, usually relatively can reduce the flow of beta-methylnaphthalene stream, but will reduce the efficiency of reaction like this.
The present invention also finds can with the thinner as beta-methylnaphthalene stream of beta-methylnaphthalene stream and the reacted part crude product stream of oxide water solution stream (replacing using cycling stream below) safety, the vitamin K at 55 ~ 65 DEG C and in the sufficiently long time in (such as 5 hours) cycling stream
3oxidizing reaction can not be there is further with oxide compound, and in cycling stream unreacted oxide compound still can with beta-methylnaphthalene generation oxidizing reaction, the flow of oxide water solution stream can be saved accordingly.Technician can manipulate the concentration of beta-methylnaphthalene in reaction solution stream very easily, only needs adjustment reactant flow flow, oxide water solution stream flow and beta-methylnaphthalene stream flow, just can guarantee beta-methylnaphthalene with maximum limit to vitamin K
3transform:
Oxide water solution stream comprises sodium dichromate 99 and sulfuric acid, CrO
3content is 200 ~ 350g/L, and sulfuric acid content is 400 ~ 450g/L, and the throughput ratio of oxide water solution stream and beta-methylnaphthalene stream is 7 ~ 11:1, and the throughput ratio of beta-methylnaphthalene and reaction solution stream is 1:900 ~ 1300.Make beta-methylnaphthalene when carrying out cooling reaction, the volume by volume concentration of beta-methylnaphthalene in reaction solution stream is 0.8 ~ 1.1L/m
3.
A kind of vitamin K of the present invention
3preparation method obtain at least 58% vitamin K
3yield, and the vitamin K of preparation
3stable yield, technician does not need, according to the particular case of reaction, repeatedly to regulate various reaction parameter.
On the basis of the present invention program, reaction solution flows to the time of the conversion of crude product stream often rapidly, and reactant flow is in the process being converted into crude product stream, beta-methylnaphthalene is totally consumed light usually, heat can not be produced again, therefore cooling is stopped in time, the temperature of retaining part crude product stream (being also cycling stream), the state of temperature required by reaction can be entered fast after making it mix with beta-methylnaphthalene stream and oxide water solution stream, favourable, the present invention finds that the time cooling reaction can control at 10 ~ 15s, can guarantee that the beta-methylnaphthalene in reaction solution stream is consumed light like this, also cooling reaction can be stopped timely.
Further, The present invention gives the parameter designing scheme of optimization, be designed to 1:1000 ~ 1100 by the throughput ratio of beta-methylnaphthalene and reaction solution stream in a step.
Present invention also offers one and realize described vitamin K
3the device of preparation method, this device comprise carry out combination cooling mixing tank, carry out cooling the tubulation retort of reaction, the separating-purifying parts carrying out step c, temperature-controlled member and flow control component;
Described mixing tank by the tubulation in tubulation retort and separating-purifying members, the tubulation parallel communication in described mixing tank and tubulation retort, the circulation end that described mixing tank is provided with feed end, discharge end and is communicated with the tubulation in tubulation retort;
Described flow control component comprises the reaction solution stream flow director being arranged on discharge end and the oxide water solution stream flow director being arranged on feed end and beta-methylnaphthalene stream flow director;
Described tubulation retort is provided with flow inlet and water export, and described temperature-controlled member comprises thermometric end and is arranged on thermometer in tubulation, is communicated with the flow director of cooling water source and flow inlet and takes into account with temperature the pilot circuit that flow director is electrically connected.
The flow of beta-methylnaphthalene stream and oxide water solution stream is controlled by beta-methylnaphthalene stream flow director and oxide water solution stream flow director respectively, enter mixing tank short mix by feed end and become reaction solution stream, the tubulation passed in tubulation retort by discharge end immediately cools reaction and forms crude reaction stream, subsequent portion crude reaction stream (cycling stream) reenters mixing tank by mixing tank circulation end, and rest part crude reaction flows to into separating-purifying parts.
The cooling of tubulation is completed through flow inlet and water export by the cooling-water flowing of cooling water source, and reaction solution stream is cooled in tubulation to the temperature control of reaction, can be completed by temperature-controlled member, the thermometer be arranged in tubulation sends temperature signal in real time to pilot circuit, when the temperature varies, regulated the flow of water coolant by pilot circuit control flow check amount controller, thus can guarantee to cool reaction carrying out stable in the temperature range (55 ~ 65 DEG C) of the present invention's setting.
Vitamin K is prepared in beta-methylnaphthalene oxidation
3reaction should carry out in tubulation retort as much as possible, in fact, because beta-methylnaphthalene stream exists such risk with oxide water solution stream in mixing of mixing tank, namely there is oxidizing reaction when mixing with oxide water solution stream in beta-methylnaphthalene stream, therefore need to cool mixing tank on the one hand, prevent outside snperoxiaized generation, also need on the other hand to make to be oxidized when few beta-methylnaphthalene is that oxide water solution stream mixes as far as possible, technician can guarantee on reaction efficiency and the basis that mixes, the mixing of beta-methylnaphthalene stream and oxide water solution stream is completed in enough little space, thus reduce beta-methylnaphthalene stream and oxide water solution stream mixed uniformly time, turbine agitator mixing tank being divided into the hybrid chamber carrying out combination cooling and the torus receiving crude product stream such as can be set in described mixing tank, and by the fixing fabric structure of hybrid chamber at 0.1m
3below.
In addition, the bore of tubulation can control, between 15 ~ 25mm so that under the prerequisite improving cooling efficiency, to ensure that the circulation of reaction solution stream is smooth and easy.
Accompanying drawing explanation
Fig. 1 is the structural representation of the device (not showing separating-purifying parts) of a kind of embodiment of the present invention.
Fig. 2 is the structural representation of the tubulation retort in the device of a kind of embodiment of the present invention shown in Fig. 1.
Embodiment
See Fig. 1, one prepares vitamin K
3device, comprise mixing tank 5, tubulation retort 13, separating-purifying parts, temperature-controlled member and flow control component; Described mixing tank 5 by the tubulation in tubulation retort 13 and separating-purifying members, the tubulation parallel communication in described mixing tank 5 and tubulation retort 13.
Described tubulation retort 13 is provided with flow inlet 18 and water export 20, described row temperature-controlled member comprises the pilot circuit that thermometric end is arranged on thermometer 15 in tubulation, is communicated with cooling water source and the flow director 14 of flow inlet 18 and is electrically connected with thermometer 15 and flow director 14, pilot circuit can be set directly in thermometer 15, and such thermometer 15 is directly electrically connected with flow director 14.
Described mixing tank 5 is provided with that mixing tank 5 inside is divided into hybrid chamber 8(volume is 0.1m
3) and the turbine agitator 7 of torus 10, hybrid chamber 8 is provided with feed end 25 and discharge end 9, and torus 10 is provided with the circulation end 26 that is communicated with the tubulation in tubulation retort 13 and the spillway 3 with separating-purifying members.
Described flow control component comprises the reaction solution stream flow director 16 being arranged on discharge end 9 and the aqueous oxidizing stream flow director 1 being arranged on feed end 9 and beta-methylnaphthalene stream flow director 2.
Described mixing tank 5 overcoat has the cooling jacket having water-in 19 and water outlet 21, thus can be the same with described temperature-controlled member, for mixing tank 5 arranges mixing tank temperature-controlled member, described mixing tank temperature-controlled member comprises the pilot circuit that thermometric end is positioned at the mixing tank thermometer 11 of hybrid chamber 8, cooling jacket flow director 12 and is electrically connected with mixing tank thermometer 11 and cooling jacket flow director 12, and water-in 19 is communicated with water source by cooling jacket flow director 12.
See Fig. 2, tubulation (bore is 25mm) and row's dividing plate 30 is provided with in described tubulation retort 13, for strengthening fixed effect, with dividing plate fixed link 31, dividing plate 30 fixedly can be stringed together, described dividing plate 30 is provided with the current mouth supplying water and flow through, thus current can be made in zigzag baffling in tubulation retort 13, the increase time of flow of current in tubulation retort 13.
The bottom of tubulation retort 13 is provided with temperature-measuring port 32, conveniently grasp the temperature of reaction solution stream in tubulation, can the thermometric end of thermometer 15 be placed in tubulation, the inlet end of such as tubulation and/or the exit end of tubulation, so that the placement of thermometer 15 thermometric end.
Embodiment 1: a kind of vitamin K
3preparation method, comprising:
1. by beta-methylnaphthalene stream, oxide water solution stream and cycling stream combination cooling forming reactions liquid stream:
Open blow-off valve 6, flow director 14, cooling jacket flow director 12 and turbine agitator 7, regulate oxide water solution stream flow director 1 and beta-methylnaphthalene stream flow director 2, the flow of oxide water solution stream is made to be 800L/h, the flow of beta-methylnaphthalene stream is 85L/h, namely the throughput ratio of oxide water solution stream and beta-methylnaphthalene stream is 9.41:1, and oxide water solution stream and beta-methylnaphthalene flow to and be uniformly mixed rear forming reactions liquid stream into hybrid chamber 8;
2. continue to form crude product stream to reaction solution stream cooling reaction:
When in mixing tank 5, the liquid level of reaction solution reaches overflow port 3, open transferpump 17, reaction solution flows through transferpump 17 and squeezes into tubulation retort 13, design cooling temperature of reaction is 60 DEG C, adjust flux controller 14 and cooling jacket flow director 12, the reading of thermometer 15 and mixing tank thermometer 11 is made to be 58 ~ 62 DEG C, butterfly valve (reaction solution stream flow director 16) aperture be 45 ° (now, the throughput ratio of beta-methylnaphthalene and reaction solution stream is 1:941 ~ 1000), the reaction times (also namely reaction solution flows through the time of tubulation) controls at 14.0 ~ 15.3s;
3. from crude product stream, vitamin K is separated
3:
The circulation end 26 flowing through mixing tank 5 from the crude reaction of tubulation retort 13 outflow enters mixing tank torus 10, part crude product stream then enters separating-purifying parts by overflow port 3, by cooling, filters, wash to obtain wet β-vitamin k4 stream 105kg/h, pure 57.8kg/h.
And rest part crude product stream (cycling stream) reenters hybrid chamber 8 with oxide water solution stream and beta-methylnaphthalene stream through turbine agitator 7 mixes, from and 1. step.
Embodiment 2:
With the difference of embodiment 1, embodiment 2 is only that oxide water solution flow is 1050L/h, beta-methylnaphthalene flow is 100L/h, aperture 70 ° (now for butterfly valve (reaction solution stream flow director 16), the throughput ratio of beta-methylnaphthalene and reaction solution stream is 1:1000 ~ 1050), wet β-the vitamin k4 obtained is 131kg/h, pure 69.5kg/h.
Embodiment 3:
With the difference of embodiment 1, embodiment 3 is only that oxide water solution flow is 1200L/h, beta-methylnaphthalene flow is 110L/h, aperture 90 ° (now for butterfly valve (reaction solution stream flow director 16), the throughput ratio of beta-methylnaphthalene and reaction solution stream is 1:1045 ~ 1091), wet β-the vitamin k4 obtained is 143kg/h, pure 75.7kg/h.
The response situation of embodiment 1-3 and the results are shown in following table:
Wherein:
；
。
Claims (5)
1. a vitamin K
3preparation method, comprising:
A. by beta-methylnaphthalene stream, oxide water solution stream and cycling stream combination cooling forming reactions liquid stream;
B. continue to form crude product stream to reaction solution stream cooling reaction;
C. from crude product stream, vitamin K is separated
3;
Part crude product stream in described b step is reused for a step as cycling stream; In a step, oxide water solution stream comprises sodium dichromate 99 and sulfuric acid, CrO
3content is 200 ~ 350g/L, and sulfuric acid content is 400 ~ 550g/L, and the throughput ratio of oxide water solution stream and beta-methylnaphthalene stream is 7 ~ 11:1, and the throughput ratio of beta-methylnaphthalene and reaction solution stream is 1:900 ~ 1300; The reaction fluid temperature of described b step controls at 55 ~ 65 DEG C, the thinner as beta-methylnaphthalene stream of described cycling stream safety, and make beta-methylnaphthalene when carrying out cooling reaction, the volume by volume concentration of beta-methylnaphthalene in reaction solution stream is 0.8-1.1L/m
3.
2. a kind of vitamin K according to claim 1
3preparation method, it is characterized in that the throughput ratio of beta-methylnaphthalene and reaction solution stream in a step is 1:1000 ~ 1100.
3. a kind of vitamin K according to claim 1
3preparation method, it is characterized in that the cooling reaction times of b step controls at 10 ~ 15s.
4. implement vitamin K as claimed in claim 1 for one kind
3the device of preparation method, comprises the mixing tank carrying out combination cooling, the tubulation retort carrying out cooling reaction, separating-purifying parts, temperature-controlled member and flow control component;
Described mixing tank by the tubulation in tubulation retort and separating-purifying members, the tubulation parallel communication in described mixing tank and tubulation retort, the circulation end that described mixing tank is provided with feed end, discharge end and is communicated with the tubulation in tubulation retort;
Described flow control component comprises the reaction solution stream flow director being arranged on discharge end and the aqueous oxidizing stream flow director being arranged on feed end and beta-methylnaphthalene stream flow director;
Described tubulation retort is provided with flow inlet and water export, and described temperature-controlled member comprises thermometric end and is arranged on thermometer in tubulation, is communicated with the flow director of cooling water source and flow inlet and takes into account with temperature the pilot circuit that flow director is electrically connected;
Be provided with turbine agitator mixing tank being divided into the hybrid chamber carrying out combination cooling and the torus receiving crude product stream in described mixing tank, the volume of described hybrid chamber is less than 0.1m
3.
5. one according to claim 4 prepares vitamin K
3device, it is characterized in that the bore of described tubulation is 15 ~ 25mm.
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| CN201310135494.XA CN103254056B (en) | 2013-04-18 | 2013-04-18 | A kind of vitamin K 3preparation method and device |
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| CN201310135494.XA CN103254056B (en) | 2013-04-18 | 2013-04-18 | A kind of vitamin K 3preparation method and device |
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| CN103254056B true CN103254056B (en) | 2016-02-24 |
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| CN111892490A (en) * | 2020-06-18 | 2020-11-06 | 兄弟科技股份有限公司 | Ce4+Method for preparing beta-menadione and its derivative menadione sodium bisulfite as oxidant |
| CN112778112A (en) * | 2021-01-04 | 2021-05-11 | 兄弟科技股份有限公司 | Method and device for synthesizing vitamin K3 |
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| Title |
|---|
| Cr（VI）氧化2-甲基萘制备2-甲基-1,4-萘醌的工艺研究;宋盛盈等;《精细石油化工》;20010731(第4期);第10-12页 * |
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