CN104628599A - Method applied to industrial continuous production of hydroxy acetonitrile - Google Patents
Method applied to industrial continuous production of hydroxy acetonitrile Download PDFInfo
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- CN104628599A CN104628599A CN201410460442.4A CN201410460442A CN104628599A CN 104628599 A CN104628599 A CN 104628599A CN 201410460442 A CN201410460442 A CN 201410460442A CN 104628599 A CN104628599 A CN 104628599A
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- LTYRAPJYLUPLCI-UHFFFAOYSA-N glycolonitrile Chemical compound OCC#N LTYRAPJYLUPLCI-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000010924 continuous production Methods 0.000 title abstract 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 493
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims abstract description 147
- 239000002994 raw material Substances 0.000 claims abstract description 19
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 122
- 239000007788 liquid Substances 0.000 claims description 113
- 238000010521 absorption reaction Methods 0.000 claims description 96
- 238000000605 extraction Methods 0.000 claims description 46
- 239000012530 fluid Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 9
- 238000007865 diluting Methods 0.000 abstract description 4
- 230000011987 methylation Effects 0.000 abstract 1
- 238000007069 methylation reaction Methods 0.000 abstract 1
- 229960004279 formaldehyde Drugs 0.000 description 140
- 235000019256 formaldehyde Nutrition 0.000 description 139
- 239000000047 product Substances 0.000 description 99
- 230000009102 absorption Effects 0.000 description 78
- 239000007789 gas Substances 0.000 description 35
- 230000003068 static effect Effects 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000003513 alkali Substances 0.000 description 11
- XLJMAIOERFSOGZ-UHFFFAOYSA-N cyanic acid Chemical compound OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
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- 230000001105 regulatory effect Effects 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000002826 coolant Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- 241000857212 Varanus nebulosus Species 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
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- 229920002866 paraformaldehyde Polymers 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
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- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- XBVNDLWWXOWJFY-UHFFFAOYSA-N C=O.OC#N Chemical compound C=O.OC#N XBVNDLWWXOWJFY-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 239000000498 cooling water Substances 0.000 description 1
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- 230000009615 deamination Effects 0.000 description 1
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- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- BSRDNMMLQYNQQD-UHFFFAOYSA-N iminodiacetonitrile Chemical compound N#CCNCC#N BSRDNMMLQYNQQD-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 239000011259 mixed solution Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method applied to industrial continuous production of hydroxy acetonitrile. The method comprises the following steps: diluting a high-concentration formaldehyde raw material into low-concentration formaldehyde by using qualified hydroxy acetonitrile by virtue of a hydrocyanic acid hydroxyl methylation method, reacting the low-concentration formaldehyde with hydrocyanic acid to prepare a qualified hydroxy acetonitrile product; and extracting one part of the qualified hydroxy acetonitrile product as product collection and extracting the other part of the qualified hydroxy acetonitrile product as a circulation solution for diluting the continuously supplied high-concentration formaldehyde into low-concentration formaldehyde, continuously reacting the low-concentration formaldehyde with the continuously supplied hydrocyanic acid, and circulating in the manner to continuously produce the qualified hydroxy acetonitrile product. By virtue of the method, the industrial continuous production of the hydroxy acetonitrile is implemented; the produced hydroxy acetonitrile product is high in yield and extremely low in formaldehyde residue; the high-concentration industrial formaldehyde can be directly used; and the hydrocyanic acid serving as the raw material can be fully utilized.
Description
Technical field
The present invention relates to the method for suitability for industrialized production hydroxyacetonitrile, be specifically related to a kind of method of continuous seepage hydroxyacetonitrile.
Background technology
Hydroxyacetonitrile, have another name called glycolonitrile or formaldehyde cyanalcohol, colourless to light yellow liquid, severe toxicity, the mixed gas containing prussic acid can be volatilized in the container opened wide, can dissolve some metals and generate complex compound, dissolve in ethanol, ether, it in field application such as chemical industry, dyestuff, medicine, agricultural chemicals widely.
The preparation method of hydroxyacetonitrile mainly contains acetonitrile oxidation style and prussic acid methylolation method.The technique of prussic acid methylolation method is specially: liquid formaldehyde and finite concentration hydrocyanic acid gas, under suitable acid-base environment, directly carry out addition reaction and generate hydroxyacetonitrile in atmospheric pressure device.Although the composition principle of prussic acid methylolation method and experimental implementation are all studied very thorough, in commercial process, still there is following problem:
(1) raw material: in industrial production, the industrial formol concentration obtained is general higher, itself and prussic acid direct reaction, often can not react completely, cause in hydroxyacetonitrile product and remain more formaldehyde, and then affect other reactions that hydroxyacetonitrile participates in further, cause a large amount of generations of side reaction, impurity.
(2) product and pH: the chemical property of hydroxyacetonitrile is very active, temperature variation or acid-basicity change very easily cause as side reactions such as hydrolysis, condensation, esterifications, generate the multiple derivatives such as oxyacetic acid, iminodiacetonitrile, Serine, glycine.Prepare in the process of hydroxyacetonitrile at formaldehyde absorption prussic acid, require to react under weakly alkaline and could comparatively fast carry out (as adopted catalyzer S-WAT, sodium bicarbonate etc.); But hydroxyacetonitrile is unstable under high ph conditions, in routine preservation, the pH of hydroxyacetonitrile system is extremely low.That is, the time that the hydroxyacetonitrile of generation stops in reaction system is longer, and the chance changing into by product is just higher.
(3) reaction times: because this chemical reaction is reversible, and as described in (2) the active character of hydroxyacetonitrile, and the autohemagglutination ability that formaldehyde and prussic acid are stronger separately in the basic conditions, the reaction times is longer, side reaction is more, and by product is more.But the reaction times is short, conversion rate of products but can be made low, cause quality product defective equally.
(4) temperature of reaction: the process of formaldehyde absorption prussic acid is a thermopositive reaction, must cool in time, to avoid, because fiercely reaction causes the play liter of temperature of reaction and the generation of side reaction, making darkening of reaction solution.
In actual production, for improving feed stock conversion, people usually adopt and extend formaldehyde and the way in prussic acid reaction times.But as previously mentioned, reaction system exists pH, temperature, time bad control, the problems such as product instability, by product and side reaction are many, therefore quality product is difficult to ensure.In addition, because the concentration of formaldehyde fed intake is high, in final reaction liquid, the residual quantity of formaldehyde also often exceeds standard, and these residual formaldehyde do not have effective minimizing technology, and the application of the hydroxyacetonitrile product of acquisition is also restricted.For the problem of high density, just think and high-concentration formaldehyde can be diluted to low concentration formaldehyde, as diluted with water, but the membership that adds of water reduces speed of reaction, and water can not effectively be removed in the product obtained, cause the concentration of hydroxyacetonitrile product low, still limit its application.
Wu little Dong describes the industrial process of prussic acid methylolation legal system for hydroxyacetonitrile in " hydroxyacetonitrile produce in the generation of polymkeric substance and process " literary composition.This industrial process is continuous processing: by feed hydrogen cyanic acid and formaldehyde with the mode charging of two dropping, by gas-liquid cocurrent absorption reaction continuous seepage hydroxyacetonitrile.In flow reactor, adding of gaseous hydrocyanic acid is continuous, and liquid phase (mixed solution of formaldehyde and hydroxyacetonitrile) is recycled injecting reactor by recycle pump and absorbs prussic acid, is migrated out reactor immediately after reaction reaches terminal.When judging the terminal of reaction, with formaldehyde mass concentration for index, when namely the concentration of formaldehyde is < 5g/L, reaction reaches terminal.In addition, the temperature of reaction needs to control at 15-22 DEG C, and pH value is between 4-7.This technique is when trying one's best optimizing materials, reaction conditions, but still by reaction in produce polymkeric substance worry, this is the unvanquishable inherent defect of this technological design: in process of production, although the charging of raw material liquid and gas is all continuous print, but discharging is but interval, be not continuous seepage truly (raw material is sent into continuously, react and carry out the continuous extraction with product continuously); Along with the carrying out of reaction, the hydroxyacetonitrile of accumulation gets more and more, and reduces speed of reaction on the one hand, reduces feed stock conversion; On the other hand, at reaction conditions, easily there is again polymerization or decompose in the product of generation, reduces quality product.
Therefore, when utilizing Industrial raw material and scale operation, still lack the production technique of hydroxyacetonitrile of a kind of real continuous print height yield, high-quality.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of method of industrialization continuous seepage hydroxyacetonitrile, the product residual formaldehyde that the method obtains is low, achieves the industrialization of hydroxyacetonitrile, continuous prodution.
For achieving the above object, technical scheme of the present invention is:
The method of industrialization continuous seepage hydroxyacetonitrile, the production of described hydroxyacetonitrile adopts prussic acid methylolation method, with qualified hydroxyacetonitrile, high-concentration formaldehyde raw material is diluted to low concentration formaldehyde, low concentration formaldehyde reacts obtained qualified hydroxyacetonitrile product again with prussic acid; Described qualified hydroxyacetonitrile product section extraction is as product-collecting, the high-concentration formaldehyde continuing to fill into is diluted to low concentration formaldehyde as circulation fluid by another part extraction, low concentration formaldehyde continues to react with the prussic acid continuing to fill into, repeat aforementioned operation, namely obtain qualified hydroxyacetonitrile product continuously.
In such scheme, owing to high-concentration formaldehyde being diluted to lower concentration with qualified hydroxyacetonitrile product, after having reacted, in product, almost no longer there is the residual of formaldehyde, directly also there is not the problem of separation and purification with hydroxyacetonitrile dilution raw material.Continue to fill into high-concentration formaldehyde and prussic acid, continue extraction hydroxyacetonitrile product, also just achieve continuous prodution.
The described qualified hydroxyacetonitrile used first, can be that a small amount of high-concentration formaldehyde and prussic acid fully react rear obtained qualified hydroxyacetonitrile, because material quantity is few, reaction times is shorter, also be unlikely to produce more by product, minimum on the impact of the hydroxyacetonitrile quality product that follow-up continuous seepage obtains; Or qualified hydroxyacetonitrile is that the production of upper batch products obtains; Or qualified hydroxyacetonitrile is obtained by additive method synthesis.Whether qualified the defining of hydroxyacetonitrile, then determine according to concrete customer demand, as claim residual formaldehyde < 5g/L, the hydroxyacetonitrile product of prussic acid residual quantity < 2g/L is qualified, and for example strictlyer also require that residual formaldehyde is 0, namely formaldehyde does not detect just for qualified.
In the present invention, described high-concentration formaldehyde and low concentration formaldehyde are before and after relative dilution, and namely before dilution is high-concentration formaldehyde, and after dilution is low concentration formaldehyde.At present, the concentration of industrial formol is generally 10%-50%wt (per-cent in mass), and the concentration of formaldehyde as adopted methanol oxidation method to obtain is generally 37%.Therefore, the present invention, in industrial implementation, generally regards the formaldehyde of concentration >=10% as high-concentration formaldehyde, and regards the formaldehyde of concentration < 10% as low concentration formaldehyde.For adapting with the concentration of industrial hydrogen cyanic acid gas, the speed of formaldehyde absorption prussic acid is made to reach preferable states, and residual as far as possible little of formaldehyde after making reaction, the formaldehyde of lower concentration is preferably 0.05%-5%wt, more preferably 0.2%-0.4%wt.
Further, the reaction of described formaldehyde and prussic acid is that two-stage absorbs hybrid reaction, and the method comprises the following steps:
A, first order reaction: absorb hydrocyanic acid gas with low concentration formaldehyde and obtain first order absorption liquid, namely qualified hydroxyacetonitrile product;
B, second order reaction: absorb in first order reaction with high-concentration formaldehyde and do not absorb prussic acid completely, obtain secondary absorption liquid;
C, circulation: the part primary absorption liquid of extraction steps A gained is product, the secondary diluted absorption solution of step B gained is become low concentration formaldehyde as circulation fluid by extraction another part first order absorption liquid, and low concentration formaldehyde is recycled in steps A the absorption continuing on for prussic acid; Fill into hydrocyanic acid gas continuously in steps A, in step B, fill into high-concentration formaldehyde continuously, the operation of repeating step A, B, C, namely obtain qualified hydroxyacetonitrile product continuously.
The response characteristic of formaldehyde and prussic acid determines under low concentration of formaldehyde, and assimilation effect can be relatively poor, and continuous processing requires to react under low concentration of formaldehyde and just can obtain qualified hydroxyacetonitrile product.The present invention is by two-stage absorption reaction, and first order reaction adopts low concentration formaldehyde to carry out absorption and obtains qualified product, and second order reaction then adopts the formaldehyde of high density to absorb tail gas, to ensure that prussic acid absorbs completely; Secondary absorbs that the secondary absorption liquid formaldehyde content obtained is high, and hydroxyacetonitrile content is low, reacts so beat the absorption liquid forming low concentration of formaldehyde to first order reaction system and qualified part of hydroxyl acetonitrile product (also i.e. circulation fluid) with prussic acid again.Such two-stage absorbs combination, has not only ensured to obtain qualified hydroxyacetonitrile product but also can ensure that prussic acid obtains maximized absorption.Further, the requirement of the temperature, pH etc. of the secondary absorption liquid obtained after second order reaction also convergence first order reaction gradually, carries out first order reaction after can better merging with circulation fluid.
Further, described first order reaction completes in A reactor and primary cycle tank, and described second order reaction completes in second reactor and secondary cycle tank; When reacting, the flow direction of material is: in described A reactor, pass into low concentration formaldehyde and hydrocyanic acid gas, react to obtain gas-liquid mixture, gas-liquid separation obtains first order absorption liquid and enters primary cycle tank, obtains tail gas and enters second reactor; Fill into high-concentration formaldehyde continuously in described secondary cycle tank, described high-concentration formaldehyde enters second reactor, and obtain gas-liquid mixture after reacting with the tail gas from A reactor, gas-liquid separation obtains secondary absorption liquid and enters secondary cycle tank; Described primary cycle tank extraction part primary absorption liquid is product, and extraction another part first order absorption liquid mixes with the part secondary absorption liquid of described secondary cycle tank extraction, is circulated in A reactor, continues to react with the hydrocyanic acid gas continuing to pass into.
Above-mentioned bonding apparatus is prepared in the method for hydroxyacetonitrile, high-concentration formaldehyde of controlling well enters the speed (generally by keeping the constant liquid level of secondary cycle tank to realize) of secondary cycle tank, first order absorption liquid (i.e. circulation fluid) and secondary absorption liquid and enters the speed that the speed of A reactor and prussic acid enter A reactor, just can realize the preparation of lasting qualified hydroxyacetonitrile.Usually, preferably controlling pure formaldehyde in first order reaction process is 0.9-1.05:1 with the ratio of the amount of substance of prussic acid.Particularly, control first order absorption liquid and secondary absorption liquid enter the flow in described A reactor, make the concentration of formaldehyde in A reactor remain on 0.05%-5%wt, more preferably 0.2%-0.4%wt.The hydrocyanic acid gas contained in the tail gas obtained after gas-liquid separation in described second order reaction is few, other foreign gases mainly in industrial hydrogen cyanic acid gas, as adopted the foreign gas in the hydrocyanic acid gas of the synthesis such as iS-One method, light oil cracking method, process by modes such as burning and/or alkali liquor absorptions, to avoid environmental pollution.
Further, described hydroxyacetonitrile, when producing, maintains whole system temperature all the time not higher than 30 DEG C.Preferably concrete: in reaction process, the temperature of system controls at 10-30 DEG C, and the temperature of secondary absorption liquid controls at 15-30 DEG C, and the temperature of qualified hydroxyacetonitrile product (first order absorption liquid) controls at 20-30 DEG C.
Further, the pH controlling system in reaction process is 6-7.5, and preferred pH is 6-7.The maintenance of this pH serves catalyzer role, and be conducive to the absorption reaction speed accelerating formaldehyde and prussic acid, it specifically by adding alkali to realize in reaction system, as added alkali with the slight alkalinity of maintenance system in secondary cycle tank.
Further, after reaction, the qualified hydroxyacetonitrile product acid adjustment of extraction is 2-3 to pH, is finished product.Acid adjustment is because hydroxyacetonitrile is unstable at a high ph, and acid specifically used is as conventional mineral acid-dilute sulphuric acid etc.
For implementing the device of above-mentioned industrialization continuous seepage hydroxyacetonitrile method, can adopt but be not limited to following apparatus system:
The device of industrialization continuous seepage hydroxyacetonitrile, the production of described hydroxyacetonitrile adopts prussic acid methylolation method, and described device comprises first order reaction unit and second order reaction unit; Described first order reaction unit comprises A reactor and primary cycle tank, and described second order reaction unit comprises second reactor and secondary cycle tank; Absorb prussic acid with low concentration formaldehyde in described A reactor and obtain gas-liquid mixture, gas-liquid separation obtains first order absorption liquid and enters primary cycle tank, obtains tail gas and enters second reactor; Fill into high-concentration formaldehyde continuously in described secondary cycle tank, described high-concentration formaldehyde enters second reactor, and obtain gas-liquid mixture after reacting with the tail gas from A reactor, gas-liquid separation obtains secondary absorption liquid and enters secondary cycle tank; Described primary cycle tank extraction part primary absorption liquid is product, and extraction another part first order absorption liquid mixes with the part secondary absorption liquid of described secondary cycle tank extraction, is circulated in A reactor.
Further, described first order reaction unit and second order reaction unit are all auxiliary is provided with refrigerating unit, for controlling the temperature of reaction system in reaction process.Described refrigerating unit concrete as, cooling water pipeline system being set in equipment interlayer, by controlling the size passing into cold water or icy salt solution flow, carrying out operating device internal temperature.
Further, be also provided with incineration system, for carrying out burning disposal to the tail gas after gas-liquid separation in second order reaction unit.Described incineration system is concrete as incinerator.In addition, alkali liquor absorption device is adopted also can to process tail gas.
Further, be also provided with product acid-regulating tank, it is for receiving the part primary absorption liquid of primary cycle tank extraction, and is finished product after acid adjustment.Low pH contributes to the stable of product hydroxyacetonitrile.
Further, in described device, the transfer of material and extraction are carried out continuously by pipeline and pump.Continuous, the reaction process that can achieve that industrial raw material enters like this continuously and product extraction continuous.
With regard to pipeline, concrete as, A reactor is provided with prussic acid synthetic gas intake ducting, being provided with material pipe to be connected with primary cycle tank (for carrying qualified hydroxyacetonitrile product (first order absorption liquid) to primary cycle tank), being provided with exhaust pipe and being connected with second reactor; Secondary cycle tank is provided with high-concentration formaldehyde feed pipe, be provided with alkali lye feeding tube, be provided with material pipe to be connected with second reactor (for receiving secondary absorption liquid), be provided with second order reaction spray piping be connected with second reactor (for carry formaldehyde in other words secondary absorption liquid to second reactor circulating reaction), be provided with formaldehyde feeding tube and be connected with A reactor (for transport portion secondary absorption liquid to A reactor); Described primary cycle tank is provided with first order reaction spray piping and is connected with A reactor (for transport portion first order absorption liquid to A reactor), is provided with product extraction pipeline and is connected with acid-regulating tank (extraction for qualified hydroxyacetonitrile product (part primary absorption liquid)).
With regard to pump, concrete as, establish first order reaction recycle pump (for transport portion first order absorption liquid to A reactor) between primary cycle tank and A reactor; Establishing second order reaction recycle pump (for carrying formaldehyde to second reactor) between secondary cycle tank and second reactor, between secondary cycle tank and A reactor, establishing formaldehyde charge pump (for transport portion secondary absorption liquid to A reactor); Establish product extraction pump between acid-regulating tank and finished product storage tank, between acid-regulating tank and primary cycle tank, establish sour volume pump; Alkali volume pump is provided with in alkali lye feeding tube.
In addition, in described device, can also static mixer be set, be beneficial to the abundant mixing of feed liquid.Concrete as, first order reaction spray piping (transport portion first order absorption liquid) and formaldehyde feeding tube (transport portion secondary absorption liquid) come together in static mixer, input A reactor again and react after feed liquid fully mixes; High-concentration formaldehyde feed pipe and alkali lye feeding tube come together in static mixer, input secondary cycle tank again after adjusting pH; Between primary cycle tank and acid-regulating tank, also static mixer is set, for acid and fully the mixing of product (first order absorption liquid), with the pH regulating product extremely stable.
In addition, described A reactor and second reactor can also arrange cyclonic separator, for the separation of gas-liquid mixture.
In described device, repeat no more the setting of pipeline, pump and other chemical industry supplementary units, as long as on the basis meeting aforementioned function, what those skilled in the art made suitably deletes, replace, merge and be included in design of the present invention.Certainly, the transfer of artificial or other modes of described partial material, as long as when not affecting reaction and carrying out extraction continuous in product continuously, is also that continuous print is in the production carrying out hydroxyacetonitrile.
Beneficial effect of the present invention is:
(1) method of the production hydroxyacetonitrile of the present invention's employing, achieve industrialization, continuous prodution, the hydroxyacetonitrile product yield of acquisition is high, and residues of formaldehyde is extremely low, and directly can use the industrial formol of high density, feed hydrogen cyanic acid is also fully used.
(2) by the setting of second order reaction, pre-reaction has been carried out to the formaldehyde raw material of high density, absorb again unreacted hydrocyanic acid gas completely further, both be beneficial to raw material and proceed to the continuous reaction of first order reaction System relays, take full advantage of again prussic acid raw material, decrease exhaust emissions, high-efficiency environment friendly.
(3) creationary the diluent of product hydroxyacetonitrile as raw material to be used, both the concentration of raw material formaldehyde had been turned down to meet reaction requirement, turn avoid reaction interference and follow-up separating-purifying problem that other solvent cuts bring, directly obtain qualified product; Raw material continues to add, and product continues extraction, achieves continuous seepage, it also avoid the problem of the multiple side reaction of product accumulation.
Accompanying drawing explanation
Fig. 1 is equipment and the material flow figure of industrialization continuous seepage hydroxyacetonitrile device of the present invention.
Embodiment
For avoiding confusion, the following partial words lexical or textual analysis mentioned is as follows:
First order absorption liquid: refer to from A reactor extraction and enter the qualified hydroxyacetonitrile product primary cycle tank.First order absorption liquid from primary cycle tank part extraction as product-collecting; Another part is low concentration formaldehyde as circulation fluid for diluting secondary absorption liquid, and the low concentration formaldehyde obtained absorbs prussic acid again in A reactor.
Secondary absorption liquid: refer to extraction from second reactor and enter the formalin in secondary cycle tank, it contains the formaldehyde of higher concentration and a small amount of hydroxyacetonitrile.The extraction of secondary absorption liquid part, and after being diluted to low concentration formaldehyde by first order absorption liquid, then prussic acid is absorbed in A reactor; After another part mixes with the high-concentration formaldehyde continuing to fill into, be recycled in second reactor and absorb residual prussic acid.
As shown in Figure 1, the device of a kind of industrialization continuous seepage hydroxyacetonitrile of the present invention, comprises first order reaction unit and second order reaction unit; Described first order reaction unit comprises A reactor 3 and primary cycle tank 2, and described second order reaction unit comprises second reactor 4 and secondary cycle tank 5; Also be provided with product acid-regulating tank 1, product extraction pump 6, first order reaction recycle pump 7, formaldehyde charge pump 8 (being also secondary absorption liquid charge pump), second order reaction recycle pump 9, cyclonic separator 10, static mixer 11,12 and 13, alkali volume pump and sour volume pump in addition.
Being set to of pipeline in described device: A reactor 3 is provided with HCN synthetic gas intake ducting a, being provided with material pipe to be connected with primary cycle tank 2 (for carrying qualified hydroxyacetonitrile product (first order absorption liquid) to primary cycle tank 2), being provided with exhaust pipe and being connected with second reactor 4; Secondary cycle tank 5 is provided with high-concentration formaldehyde feed pipe e, be provided with alkali lye feeding tube, be provided with material pipe to be connected with second reactor 4 (for receiving secondary absorption liquid), be provided with second order reaction spray piping d be connected with second reactor 4 (for carry formaldehyde in other words secondary absorption liquid to second reactor 4 circulating reaction), be provided with formaldehyde feeding tube c and be connected with A reactor 3 (for transport portion secondary absorption liquid to A reactor 3); Described primary cycle tank 2 is provided with first order reaction spray piping b and is connected with A reactor 3 (for transport portion first order absorption liquid to A reactor 3), is provided with product extraction pipeline f and is connected with acid-regulating tank 1 (extraction for qualified hydroxyacetonitrile product); Acid-regulating tank 1 is provided with sour feeding tube, is provided with finished product extraction pipeline g and hydroxyacetonitrile finished product is delivered to finished product storage tank.
Product extraction pump 6 is located in finished product extraction pipeline g, and first order reaction recycle pump 7 is located in first order reaction spray piping b, and formaldehyde charge pump 8 is located in formaldehyde feeding tube c, and second order reaction recycle pump 9 is located in second order reaction spray piping d.Wherein, first order reaction recycle pump 7 and formaldehyde charge pump 8 the function Liang Ge branch that also can be set up in parallel by a pump replaced.
Static mixer 11 mixing (furnishing is acid) for diluted acid and first order absorption liquid, static mixer 12 mixes (being delivered to A reactor 3 again as raw material) for first order absorption liquid and secondary absorption liquid, and static mixer 13 mixes (furnishing slight alkalinity) for high-concentration formaldehyde and alkali.
During the device busy of the industrialization continuous seepage hydroxyacetonitrile of Fig. 1, the material flow direction is wherein: in described A reactor 3, pass into hydrocyanic acid gas, low concentration formaldehyde in A reactor 3 absorbs prussic acid and obtains gas-liquid mixture, gas-liquid separation obtains first order absorption liquid and enters primary cycle tank 2, obtains tail gas and enters second reactor 4.High-concentration formaldehyde is filled into continuously in described secondary cycle tank 5, described high-concentration formaldehyde enters second reactor 4, gas-liquid mixture is obtained after reacting with the tail gas from A reactor, obtain secondary absorption liquid through cyclonic separator 10 gas-liquid separation and enter secondary cycle tank 5, obtain tail gas and proceed to incinerator burning disposal.Described primary cycle tank 3 extraction part primary absorption liquid is product, and after entering acid-regulating tank 1 acid adjustment, extraction stores to finished product storage tank; Described primary cycle tank 3 extraction another part first order absorption liquid mixes with the part secondary absorption liquid of described secondary cycle tank 5 extraction, is circulated in A reactor 3, continues to react with the hydrocyanic acid gas continuing to pass into.During reaction is carried out, the icy salt solution system of opening A reactor and second reactor cools.
The low concentration formaldehyde brought into use in described A reactor 3, is formed by qualified hydroxyacetonitrile diluting high-concentration formaldehyde.And the qualified hydroxyacetonitrile product first obtained, can be that a small amount of high-concentration formaldehyde and prussic acid react to residues of formaldehyde and reaches the hydroxyacetonitrile product after required value, or the hydroxyacetonitrile product obtained for upper batch production.
Referring to Fig. 1, embodiments of the invention and comparative example are described in detail, wherein the example of unreceipted actual conditions conveniently condition carry out.Feed hydrogen cyanic acid gas is the synthesis of iS-One method, and obtains after deamination process; Raw material formaldehyde is industrial formol.
Embodiment 1
10m is added in secondary cycle tank 5
3formaldehyde (concentration is 10%wt), and add adjusting PH with base value 6.0-6.5.The formaldehyde mixing up pH value in secondary cycle tank 5 is turned 2m
3to in primary cycle tank 2, then start first order reaction recycle pump 7 and second order reaction recycle pump 9 dozens circulation.HCN gas (flow velocity 22m/s) is passed in a second reactor 3 and 4 simultaneously.And by regulating the amount of water coolant to make the temperature of liquid in reaction process be 15-20 DEG C.Monitor formaldehyde residual value in primary cycle tank 2 at any time, when formaldehyde residual value reaches required value (can't check formaldehyde), obtain qualified hydroxyacetonitrile.
Then, open formaldehyde charge pump 8 and formaldehyde in secondary cycle tank 5 (or being secondary absorption liquid) is added in static mixer 12, enter A reactor 3 and react with HCN.Meanwhile, extraction part product to acid-regulating tank 1, and carries out acid adjustment by static mixer 11, and controlling product pH value is 2.5-3.0, and acid adjustment qualified product then enter finished product storage tank.Namely remaining qualified product (also first order absorption liquid) then as circulation fluid, the formaldehyde made with formaldehyde charge pump 8 mix with, as absorption liquid, HCN is absorbed.
The flow of first order reaction circulation fluid is chosen as 125m
3/ h (first order reaction recycle pump 7), second order reaction circulation fluid is 30m
3/ h (second order reaction recycle pump 9), the flow adding the secondary absorption liquid in A reactor is 4m
3/ h (formaldehyde charge pump 8).While startup formaldehyde charge pump 8, also start to add fresh formaldehyde toward 5 li, secondary cycle tank, and to control formaldehyde pH value in secondary cycle tank 5 at any time by caustic dosage be 6.5-7.0.Additional amount can ensure that the volume of secondary cycle tank 5 is not less than 6m
3.React after 5 hours and obtain product 4.54t (after folding hundred), consume HCN2.42t (after folding hundred), hydroxyacetonitrile is to HCN unit consumption 0.533t/t, hydroxyacetonitrile is 88.87% to HCN yield, the unit consumption of hydroxyacetonitrile PARA FORMALDEHYDE PRILLS(91,95) is 0.5449, in product, formaldehyde does not detect, product colour water white transparency.
Embodiment 2
5m is added in secondary cycle tank 5
3formaldehyde (concentration is 37%wt), and add adjusting PH with base value 6.5-7.0.The formaldehyde mixing up pH value in secondary cycle tank 5 is turned 2m
3to in primary cycle tank 2, then start first order reaction recycle pump 7 and second order reaction recycle pump 9 dozens circulation.HCN gas (flow velocity 22m/s) is passed in a second reactor 3 and 4 simultaneously.And by regulating the amount of water coolant to make the temperature of liquid in reaction process be 15-20 DEG C.Monitor formaldehyde residual value in primary cycle tank 2 at any time, when formaldehyde residual value reaches required value (can't check formaldehyde), obtain qualified hydroxyacetonitrile.
Then, open formaldehyde charge pump 8 and formaldehyde in secondary cycle tank 5 (or being secondary absorption liquid) is added in static mixer 12, enter A reactor 3 and react with HCN.Meanwhile, extraction part product to acid-regulating tank 1, and carries out acid adjustment by static mixer 11, and controlling product pH value is 2.5-3.0, and acid adjustment qualified product then enter finished product storage tank.Namely remaining qualified product (also first order absorption liquid) then as circulation fluid, the formaldehyde made with formaldehyde charge pump 8 mix with, as absorption liquid, HCN is absorbed.
The flow of first order reaction circulation fluid is chosen as 125m
3/ h (first order reaction recycle pump 7), second order reaction circulation fluid is 30m
3/ h (second order reaction recycle pump 9), the flow adding the secondary absorption liquid in A reactor is 1m
3/ h (formaldehyde charge pump 8).While startup formaldehyde charge pump 8, also start to add fresh formaldehyde toward 5 li, secondary cycle tank, and to control formaldehyde pH value in secondary cycle tank 5 at any time by caustic dosage be 6.5-7.0.Additional amount can ensure that the volume of secondary cycle tank 5 is not less than 3m
3.React after 5 hours and obtain product 4.7t (after folding hundred), consume HCN2.44t (after folding hundred), hydroxyacetonitrile is to HCN unit consumption 0.5191t/t, hydroxyacetonitrile is 91.25% to HCN yield, the unit consumption of hydroxyacetonitrile PARA FORMALDEHYDE PRILLS(91,95) is 0.5445, in product, formaldehyde does not detect, product colour water white transparency.
Embodiment 3
5m is added in secondary cycle tank 5
3the formaldehyde of (concentration is 50%wt), and add adjusting PH with base value 6.5-7.0.The formaldehyde mixing up pH value in secondary cycle tank 5 is turned 2m
3to in primary cycle tank 2, then start first order reaction recycle pump 7 and second order reaction recycle pump 9 dozens circulation.HCN gas (flow velocity 22m/s) is passed in a second reactor 3 and 4 simultaneously.And by regulating the amount of water coolant to make the temperature of liquid in reaction process be 15-20 DEG C.Monitor formaldehyde residual value in primary cycle tank 2 at any time, when formaldehyde residual value reaches required value (can't check formaldehyde), obtain qualified hydroxyacetonitrile.
Then, opening formaldehyde charge pump pump 8 is added in static mixer 12 by formaldehyde in secondary cycle tank 5 (or being secondary absorption liquid), enter A reactor 3 to react with HCN, the part of extraction simultaneously product is to acid-regulating tank 1, and carry out acid adjustment by static mixer 11, controlling product pH value is 2.5-3.0, and acid adjustment qualified product then enter finished product storage tank.Namely remaining qualified product (also first order absorption liquid) then as circulation fluid, the formaldehyde made with formaldehyde charge pump 8 mix with, as absorption liquid, HCN is absorbed.
The flow of first order reaction circulation fluid is chosen as 50m
3/ h (first order reaction recycle pump 7), second order reaction circulation fluid is 30m
3/ h (second order reaction recycle pump 9), the flow adding the secondary absorption liquid in A reactor is 1m
3/ h (formaldehyde charge pump 8).While startup formaldehyde charge pump 8, also start to add fresh formaldehyde toward 5 li, secondary cycle tank, and to control formaldehyde pH value in secondary cycle tank 5 at any time by caustic dosage be 6.5-7.0.Additional amount can ensure that the volume of secondary cycle tank 5 is not less than 3m
3.React after 5 hours and obtain product 4.4t (after folding hundred), consume HCN2.44t (after folding hundred), hydroxyacetonitrile is to HCN unit consumption 0.5545t/t, hydroxyacetonitrile is 85.43% to HCN yield, the unit consumption of hydroxyacetonitrile PARA FORMALDEHYDE PRILLS(91,95) is 0.5453, in product, formaldehyde does not detect, product colour water white transparency.
Comparative example 1
5m is added in secondary cycle tank 5
3formaldehyde (37%wt), and add adjusting PH with base value 6.5-7.0.The formaldehyde mixing up pH value in secondary cycle tank 5 is turned 2m
3to in primary cycle tank 2, then start first order reaction recycle pump 7 and second order reaction recycle pump 9 dozens circulation.HCN gas (flow velocity 22m/s) is passed in a second reactor 3 and 4 simultaneously.And by regulating the amount of water coolant to make the temperature of liquid in reaction process be 35-40 DEG C.React about 30min, product colour becomes not good merchantable, and product is polymerized.
Comparative example 2
To primary cycle tank 2, in secondary cycle tank 5, add 5m respectively
3(37%wt) formaldehyde, and add adjusting PH with base value 6.5-7.0, then start first order reaction recycle pump 7, secondary cycle pump 9 plays circulation simultaneously; Simultaneously by HCN gas successively (flow velocity 22m/s) pass in A reactor 3 and second reactor 4.The temperature of liquid in reaction process is made to be 15-20 DEG C by regulating the amount of water coolant.React after 5 hours and obtain product 4.48t (after folding hundred), consume HCN2.42t (after folding hundred), hydroxyacetonitrile is to HCN unit consumption 0.5402t/t, hydroxyacetonitrile is 87.69% to HCN yield, in product, formaldehyde does not detect, but product colour becomes Sandy, product generating portion is polymerized.
To sum up, according to many experiments, the preferred 6.5-7.0 of pH value in reaction of the present invention, the preferred 15-20 DEG C of temperature of reaction; First order reaction internal circulating load 80-130m
3/ h, preferred 120-130m
3/ h (being namely circulated to the amount of the first order absorption liquid in A reactor), second order reaction circulation fluid 25-40m
3/ h (being namely circulated to the amount of the secondary absorption liquid in second reactor).It is fixed that formaldehyde inlet amount (flow of formaldehyde feeding tube c) then looks HCN output, preferably make pure formaldehyde amount of substance in A reactor: the ratio of HCN amount of substance is 0.9-1.05:1, formaldehyde inlet amount too much can make the too high product that makes of product residues of formaldehyde value defective, has lacked and has affected assimilation effect.
What finally illustrate is, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (10)
1. the method for industrialization continuous seepage hydroxyacetonitrile, the production of described hydroxyacetonitrile adopts prussic acid methylolation method, it is characterized in that: with qualified hydroxyacetonitrile, high-concentration formaldehyde raw material is diluted to low concentration formaldehyde, low concentration formaldehyde reacts obtained qualified hydroxyacetonitrile product again with prussic acid; Described qualified hydroxyacetonitrile product section extraction is as product-collecting, the high-concentration formaldehyde continuing to fill into is diluted to low concentration formaldehyde as circulation fluid by another part extraction, low concentration formaldehyde continues to react with the prussic acid continuing to fill into, repeat aforementioned operation, namely obtain qualified hydroxyacetonitrile product continuously.
2. the method for industrialization continuous seepage hydroxyacetonitrile according to claim 1, is characterized in that: the reaction of described formaldehyde and prussic acid is that two-stage absorbs hybrid reaction, and the method comprises the following steps:
A, first order reaction: absorb hydrocyanic acid gas with low concentration formaldehyde and obtain first order absorption liquid, namely qualified hydroxyacetonitrile product;
B, second order reaction: absorb in first order reaction with high-concentration formaldehyde and do not absorb prussic acid completely, obtain secondary absorption liquid;
C, circulation: the part primary absorption liquid of extraction steps A gained is product, the secondary diluted absorption solution of step B gained is become low concentration formaldehyde as circulation fluid by extraction another part first order absorption liquid, and low concentration formaldehyde is recycled in steps A the absorption continuing on for prussic acid; Fill into hydrocyanic acid gas continuously in steps A, in step B, fill into high-concentration formaldehyde continuously, the operation of repeating step A, B, C, namely obtain qualified hydroxyacetonitrile product continuously.
3. the method for industrialization continuous seepage hydroxyacetonitrile according to claim 2, it is characterized in that: described first order reaction completes in A reactor and primary cycle tank, described second order reaction completes in second reactor and secondary cycle tank; When reacting, the flow direction of material is:
In described A reactor, pass into low concentration formaldehyde and hydrocyanic acid gas, react to obtain gas-liquid mixture, gas-liquid separation obtains first order absorption liquid and enters primary cycle tank, obtains tail gas and enters second reactor; Fill into high-concentration formaldehyde continuously in described secondary cycle tank, described high-concentration formaldehyde enters second reactor, and obtain gas-liquid mixture after reacting with the tail gas from A reactor, gas-liquid separation obtains secondary absorption liquid and enters secondary cycle tank; Described primary cycle tank extraction part primary absorption liquid is product, and extraction another part first order absorption liquid mixes with the part secondary absorption liquid of described secondary cycle tank extraction, is circulated in A reactor, continues to react with the hydrocyanic acid gas continuing to pass into.
4. the method for industrialization continuous seepage hydroxyacetonitrile according to claim 3, it is characterized in that: control first order absorption liquid and secondary absorption liquid enter the flow in described A reactor, make the mass percent of formaldehyde in A reactor remain on 0.05%-5%.
5. the method for the industrialization continuous seepage hydroxyacetonitrile according to any one of Claims 1-4, is characterized in that: described hydroxyacetonitrile, when producing, maintains whole system temperature all the time not higher than 30 DEG C.
6. the method for industrialization continuous seepage hydroxyacetonitrile according to claim 5, is characterized in that: described hydroxyacetonitrile is when producing, and in reaction process, the temperature of system controls at 10-30 DEG C, and in reaction process, the pH of system controls at 6-7.5.
7. the method for industrialization continuous seepage hydroxyacetonitrile according to claim 5, is characterized in that: described hydroxyacetonitrile is when producing, and the temperature of secondary absorption liquid controls at 15-30 DEG C, and the temperature of first order absorption liquid controls at 20-30 DEG C.
8. the method for the industrialization continuous seepage hydroxyacetonitrile according to any one of Claims 1-4, is characterized in that: described hydroxyacetonitrile is when producing, and controlling pure formaldehyde in first order reaction process is 0.9-1.05:1 with the ratio of the amount of substance of prussic acid.
9. the method for the industrialization continuous seepage hydroxyacetonitrile according to any one of Claims 1-4, is characterized in that: described high-concentration formaldehyde is industrial raw material, and wherein the mass percent of formaldehyde is 10%-50%.
10. the method for the industrialization continuous seepage hydroxyacetonitrile according to any one of Claims 1-4, is characterized in that: after reaction, the qualified hydroxyacetonitrile product acid adjustment of extraction is 2-3 to pH, is finished product.
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| CN115611754A (en) * | 2022-10-25 | 2023-01-17 | 安徽泰格生物科技有限公司 | Preparation method of sodium sarcosinate |
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