CN107129441A - A kind of catalyst and pipeline reactor of continuous production hydroxyacetonitrile - Google Patents
A kind of catalyst and pipeline reactor of continuous production hydroxyacetonitrile Download PDFInfo
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- CN107129441A CN107129441A CN201610106781.1A CN201610106781A CN107129441A CN 107129441 A CN107129441 A CN 107129441A CN 201610106781 A CN201610106781 A CN 201610106781A CN 107129441 A CN107129441 A CN 107129441A
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- reactor
- formaldehyde
- hydrogen cyanide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J14/00—Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor
- B01J14/005—Chemical processes in general for reacting liquids with liquids; Apparatus specially adapted therefor in the presence of catalytically active bodies, e.g. porous plates
Abstract
The present invention relates to a kind of method of utilization formalin and hydrogen cyanide continuous catalysis synthesis of hydroxy acetonitrile in pipeline reactor, wherein pipeline reactor is made up of 316L stainless steels.Raw material formaldehyde and catalyst（30%wt. Cymags or sodium hydrate aqueous solution）After mixing in a mixer in advance, it is introduced into the spray atomization region of reactor inlet, contact, absorb and react with coming from the hydrocyanic acid gas of hydrogen cyanide house steward, feed liquid after absorption, which enters in tubular reactor, to be continued to react, wherein spray absorber regional temperature is preferably controlled at 0 ~ 20 DEG C, preferably 15 ~ 18 DEG C；Tubular reactor temperature is preferably controlled at 0 ~ 25 DEG C, preferably 18 ~ 20 DEG C, reaction heat is removed by chilled brine or cooling water, the total residence time of material in the reactor about 2h, obtained hydroxyacetonitrile is nearly colourless transparent liquid, content 52.0%, content of formaldehyde is less than 0.05%, and cyanide ion concentration is less than 0.05%.
Description
Technical field
The invention belongs to Chemical Reaction Engineering and the application field of catalyst, and in particular to one kind utilizes hydrogen cyanide（Natural gas ammonia cracking or the hydrogen cyanide of acrylonitrile installation by-product, or other sources hydrogen cyanide）The method of manufacture hydroxyacetonitrile is reacted with formaldehyde.
Background technology
Hydroxyacetonitrile, also known as glycollic nitrile, are used as the deep processed product of hydrogen cyanide, one of the Organic Chemicals as large-tonnage yield.Hydrogen cyanide is easily vaporized, is extremely limited in use because of its low boiling point, severe toxicity, lower 25.7 DEG C of normal pressure.Hydroxyacetonitrile is by hydrogen cyanide and the product after addition reaction of formaldehyde, usually 50% aqueous solution, though it is also hypertoxic, it is comparatively easy to use, it is safe and reliable.Hydroxyacetonitrile has been widely used in the industries such as medicine, plating, ore dressing, agricultural chemicals, surfactant, can be used as production glycine, iminodiacetic acid（The intermediate of glyphosate）, malononitrile, bipseudoindoxyl dye, polyglycolic acid, glycolylurea, sodium ethylene diamine tetracetate（EDTA）Deng intermediate.
The preparation method of the hydroxyacetonitrile of document report mainly has：
1. acrylonitrile is aoxidized under using barium oxide as catalyst and vapor collective effect is made, such as United States Patent (USP) US4634789（1987）This method is disclosed, but this method also generates hydroxyl acetamide simultaneously, and the conversion ratio of reaction and the selectivity of target product are not too high, and product separation is more difficult.
2. using hydrogen cyanide and formaldehyde as raw material, hydroxyacetonitrile, such as United States Patent (USP) US2890238 are produced through addition reaction under catalyst action（Nineteen fifty-nine）、US2175805（Nineteen thirty-nine）Report respectively and use formaldehyde（Or paraformaldehyde, metaformaldehyde）With the method for industrial hydrogen cyanide synthesis of hydroxy acetonitrile in closed reactor under the conditions of cooling and 0 ~ 10 DEG C, synthetic product can distill at 1.5 ~ 1.6kPa of pressure, 125 ~ 92 DEG C of temperature obtains colourless pure hydroxyacetonitrile product, and the product need to use phosphoric acid or sulfuric acid to be stored as stabilizer.Document【Sun Fang etc., Liaoning chemical industry, 2003,32（5）：207-208】Mitsubishi chemical conversion industry company is reported to feed raw material hydrogen cyanide and formaldehyde in the way of double dropwise additions, by liquid phase reactor continuous production hydroxyacetonitrile, dropwise addition feed time is 3h, and yield can reach 99.8%, product passes through toluene azeotropic distillation, obtains the final products of purity 99.5%.The advantage of this method is that production cost is low, and product quality is stable；Have the disadvantage that hydrogen cyanide is volatile, production process security requirement is high, overhaul of the equipments has certain difficulty.Chinese patent CN200610048135.0（2006）Disclose with the hydrogen cyanide of acrylonitrile by-product and formaldehyde under catalyst, such as catalyst sodium sulfite effect, with mol ratio hydrogen cyanide:Formaldehyde:Catalyst=1:（1.0~1.5）:（0.001~0.015）, 0 ~ 40 DEG C of temperature, 1 ~ 6h of intermittent reaction, the hydroxyl acetonitrile aqueous solution product of the amount of containing≤50% can be obtained, free formaldehyde and hydrogen cyanide content are respectively less than 0.05% wherein in product.Document【Liu Lan, river, 2010, (3)：37-40】The On-Line Control Method that the falling-film absorber circulated with reaction solution continuously produces hydroxyacetonitrile is delivered, the characteristics of technique, is to realize continuous production in the way of double reactors switch in turn, one-pot is only used as initial absorption liquid using 35 ~ 37%wt. formalins during operation, until formaldehyde reaction tends to be complete, total reaction time about 4.5 ~ 5h of one-pot.
The common feature of the above method is using formalin as initial absorption liquid, addition reaction is strong exothermal reaction between hydrogen cyanide and formaldehyde, fuel factor is huge, temperature control is particularly important, and raw material hydrogen cyanide, formaldehyde, and product hydroxy acetonitrile easily itself implode, reaction temperature, catalyst amount etc. are very big on reaction influence, the removal of reaction heat and production security are sometimes more difficult to be controlled, and what the quality of product was also received very big influences.On the one hand, reaction temperature is low, reaction rate it is slow, it is necessary to reaction time it is long；On the other hand, reaction temperature is high, and reaction rate is fast, and autohemagglutination/copolymerization probability is big, and course of reaction is difficult to control to.Using sodium sulfite or other sulphite as catalyst, it has in the product of gained, and the fluctuation such as residual, and solution ph is larger, and removing residue formaldehyde is higher so that it is largely influenceed as follow-up purposes.
According to formaldehyde（Gas, -19.5 DEG C of atmospheric boiling point；37% aqueous solution, 98 DEG C of atmospheric boiling point）With hydrogen cyanide（25.7 DEG C of boiling point under normal pressure）Physical property and addition reaction generation hydroxyacetonitrile the characteristics of, preferable reactor should be the pipeline reactor of continuous operation, the material inlet of the pipeline reactor can be designed to formaldehyde and hydrogen cyanide one/or two strands of atomizing raw materials/or the shock flow type atomization absorption that crashes, advantage is that contact specific surface area is big, it is easy to remove the fuel factor of the strong exothermal reaction, reaction temperature is easily controllable, and tubular reactor can bear higher pressure（I.e. resistance to pressure is good）, produce easily controllable, product is good, steady quality.The reaction of the addition generation hydroxyacetonitrile of formaldehyde and hydrogen cyanide is the catalytic reaction under the conditions of neutral meta-alkalescence, and the preferable optional sodium hydroxide of catalyst, the aqueous solution of Cymag are used as catalyst.
The content of the invention
The purpose of the present invention is after being mixed using the industrial formol aqueous solution with catalyst Cymag or sodium hydrate aqueous solution, first it is atomized in tubular reactor, absorption comes from the hydrocyanic acid gas that hydrogen cyanide process units is sent, and being then continuously flowed into tubular reactor reacts.This law provide a kind of high conversion and in high yield, the technology and method of continuous and stable production hydroxyacetonitrile.
Brief description of the drawings：
Accompanying drawing 1, tubular reactor produced hydroxyacetonitrile device and process flow diagram
1-formaldehyde pump；2,4,9,10,12-valve；3- formaldehyde and catalyst blender；5- nozzles；Spray absorber area in 6-reactor；7-hydrogen cyanide feed pipe；8-tubular reactor；11-feed liquid circulating pump；13-hydroxyacetonitrile product storage tank
The technical solution of the present invention is as follows：
Reaction of the present invention is to utilize 37% formalin in advance and catalyst（Cymag, sodium hydroxide）Water-soluble liquid mixer（3）In quickly mix it is latter and enter reactor top, through nozzle（5）Atomization is with hydrocyanic acid gas in reactor top spray absorber area（6）Rapid contact, absorption and reaction, reaction heat therein is respectively by being arranged at spray absorber area（6）And tubular reactor（8）In cryogenic freezing salt solution or cooling water remove so that reaction controlling under certain temperature and pressure in relatively rapid generating hydroxyacetonitrile.Wherein in the atomization absorption area of the reactor（6）, easy temperature control system is at 0 ~ 20 DEG C, and the easy temperature control of tubular reactor is formed on 20 ~ 25 DEG C, and used catalyst is 30%wt. sodium cyanide solutions or 30%wt. sodium hydroxide solution, and usage amount is the 2.5 ~ 7.5% of formaldehyde inlet amount.
Embodiment
Embodiment 1
Spray absorber area in accompanying drawing（6）, its size is, H1500mm, 316L stainless steel atomizers, its volume about 1.0m3.37%wt. formaldehyde is with 49.2kmol/h amount of substance, catalyst 30%wt. sodium cyanide solutions with 38.5kg/h amount in blender（3）Middle mixing is latter and enters nozzle（5）, and with from hydrogen cyanide feed pipe（7）0.578Nm3/ h, the atomization mixing of 99.0%wt. hydrogen cyanide, are absorbed hydrogen cyanide and reacted, cooled down in spray absorber area using chilled brine, control its reaction temperature in 15 ~ 18 DEG C, the feed liquid after absorption continuously flows into the tubular reactor of 316L stainless steels naturally（8）, the size of reactor is DN100mm, 4 × L2000mm（5 stackings, which are closed, to be connected）Total length 40m, 18 ~ 20 DEG C of its reaction temperature is to be controlled by outside chilled water modulation, and material is through calculating total reaction time about 2h, export reaction product detection it is qualified after enter hydroxyacetonitrile product storage tank, supplement content 0.28%wt. sulfuric acid stabilizers as output of products out-of-bounds.Product analysis index is nearly colourless transparent liquid, and content 52.0%, content of formaldehyde is less than 0.05%, and cyanide ion concentration is less than 0.05%.
Embodiment 2
Operating condition is same as embodiment 1, and catalyst is changed into 30%wt. sodium hydroxide solutions, and the product obtained is near colourless to light green transparency liquid, and content 51.6%, content of formaldehyde is less than 0.05%, and cyanide ion concentration is less than 0.05%.
Embodiment 3
Contrast experiment：Technique productions flow is using double kettles（Enamel reacts stirred tank）Parallel operation formula is uninterruptedly continuously produced, first in a reactor（10m3）The interior a certain amount of formaldehyde of input（6500kg/ batches）And add a small amount of sodium sulfite（8.5kg/ batch）PH is adjusted to alkalescence（pH 8~9）, then in reactor progressively it is continuously added to hydrogen cyanide（550kg/h, common 4h）Reaction mass in reactor is carried out outer circulation cooling by circulating pump and moves heat by synthesis of hydroxy acetonitrile, the reaction heat of synthesis, and reaction adds stabilizer sulfuric acid after terminating（0.28%wt.）Finished product medial launder is delivered to after analysis is qualified, filling area is then sent to.Another identical size reactor starts the imitative preceding method of input formaldehyde simultaneously and each inventory is produced, to accomplish that one-pot interval, double kettles are uninterruptedly continuously produced as far as possible.The Con trolling index of product quality is near colourless to light green transparency liquid, and content 49.5% ~ 52.5%, content of formaldehyde is less than 0.05%, and cyanide ion concentration is less than 0.05%.The characteristics of method is one-pot Batch Process, and operating process influence factor is more, it is difficult to accomplish that an operating condition is stable, and the especially fluctuation such as removing residue formaldehyde, solution ph is larger so that the quality of product is affected, and it is largely influenceed as follow-up purposes.In addition, it is also possible to cause implode to be reacted, influence safety in production.
Claims (5)
1. the present invention relates to a kind of method of utilization formalin and hydrogen cyanide continuous catalysis synthesis of hydroxy acetonitrile in pipeline reactor.
2. described catalyst in claim 1, the predominantly alkali metal such as Cymag, sodium hydroxide, alkali earth metal cyanide or the hydroxide compound aqueous solution, mass concentration are 5% ~ 50%, and preferably mass concentration is 25 ~ 30%, usage amount is the 2.5% ~ 7.5% of formaldehyde inlet amount, preferably 5% or so.
3. the raw material in claim 1 is formalin, or metaformaldehyde or paraformaldehyde；Hydrogen cyanide is not less than 99.0% from natural gas ammonia thermal cracking or the by-product of light oil ammonia thermal cracking or production device for acrylic nitrile, material purity.
4. the pipeline reactor in claim 1, it is made up of Stainless steel 316 L materials, after raw material formaldehyde is pre-mixed with catalyst, into the spray atomization of reactor inlet, contact, absorb and react with coming from the hydrocyanic acid gas of hydrogen cyanide house steward, feed liquid after absorption, which enters in tubular reactor, to be continued to react, and wherein spray absorber regional temperature is preferably controlled at 0 ~ 20 DEG C, preferably 15 ~ 18 DEG C；Tubular reactor temperature is preferably controlled at 0 ~ 25 DEG C, and preferably 18 ~ 20 DEG C, reaction heat is removed by chilled brine or cooling water, and the total residence time of material in the reactor is not less than 2h.
5. the tubular reactor process condition and parameter of the continuous operation in claim 1 are：37%wt. formaldehyde:Hydrogen cyanide=2.922:1, catalyst uses 30%wt. sodium cyanide solutions, its consumption is the 5%wt. of formaldehyde inlet amount, 15 ~ 18 DEG C of the spray absorber area reaction temperature of tubular reactor, 18 ~ 20 DEG C of reaction temperature in tubular reactor, obtains nearly colourless transparent liquid, hydroxyacetonitrile content 52.0% on this condition, content of formaldehyde is less than 0.05%, and cyanide ion concentration is less than 0.05%.
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| CN201610106781.1A CN107129441B (en) | 2016-02-28 | 2016-02-28 | Catalyst and pipeline type reactor for continuously producing hydroxy acetonitrile |
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| CN201610106781.1A CN107129441B (en) | 2016-02-28 | 2016-02-28 | Catalyst and pipeline type reactor for continuously producing hydroxy acetonitrile |
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| CN107129441B CN107129441B (en) | 2021-08-13 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794346A (en) * | 2017-05-05 | 2018-11-13 | 抚顺顺特化工有限公司 | The industrial production process of hydroxyacetonitrile |
Citations (5)
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| CN1958559A (en) * | 2005-10-31 | 2007-05-09 | 安徽省安庆曙光化工(集团)有限公司 | Environmental protection clean technical method for synthesizing aminoacetic acid through fluid bed |
| CN101184717A (en) * | 2005-05-27 | 2008-05-21 | 旭化成化学株式会社 | Method for producing glycolic acid |
| CN204281648U (en) * | 2014-11-21 | 2015-04-22 | 枣阳市金鹿化工有限公司 | A kind of device utilized containing cyanogen End gas production hydroxyacetonitrile |
| CN104628598A (en) * | 2014-09-10 | 2015-05-20 | 重庆紫光化工股份有限公司 | Device for industrially producing hydroxyl acetonitrile |
| CN104725269A (en) * | 2014-11-21 | 2015-06-24 | 枣阳市金鹿化工有限公司 | Technological method for jointly preparing liquid hydrogen cyanide and hydroxynitrile |
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- 2016-02-28 CN CN201610106781.1A patent/CN107129441B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101184717A (en) * | 2005-05-27 | 2008-05-21 | 旭化成化学株式会社 | Method for producing glycolic acid |
| CN1958559A (en) * | 2005-10-31 | 2007-05-09 | 安徽省安庆曙光化工(集团)有限公司 | Environmental protection clean technical method for synthesizing aminoacetic acid through fluid bed |
| CN104628598A (en) * | 2014-09-10 | 2015-05-20 | 重庆紫光化工股份有限公司 | Device for industrially producing hydroxyl acetonitrile |
| CN204281648U (en) * | 2014-11-21 | 2015-04-22 | 枣阳市金鹿化工有限公司 | A kind of device utilized containing cyanogen End gas production hydroxyacetonitrile |
| CN104725269A (en) * | 2014-11-21 | 2015-06-24 | 枣阳市金鹿化工有限公司 | Technological method for jointly preparing liquid hydrogen cyanide and hydroxynitrile |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794346A (en) * | 2017-05-05 | 2018-11-13 | 抚顺顺特化工有限公司 | The industrial production process of hydroxyacetonitrile |
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