CN107628976B - A kind of method of clean continuous preparation 2-Hydroxy-4-methylthiobutyric acid - Google Patents
A kind of method of clean continuous preparation 2-Hydroxy-4-methylthiobutyric acid Download PDFInfo
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- PICCHNWCTUUCAQ-UHFFFAOYSA-N 2-hydroxypentanethioic s-acid Chemical compound CCCC(O)C(O)=S PICCHNWCTUUCAQ-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 45
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 486
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 241
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims abstract description 188
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 96
- 238000007670 refining Methods 0.000 claims abstract description 60
- 238000000926 separation method Methods 0.000 claims abstract description 58
- 239000007864 aqueous solution Substances 0.000 claims abstract description 54
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 48
- 239000000243 solution Substances 0.000 claims abstract description 44
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 40
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 40
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 40
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000605 extraction Methods 0.000 claims abstract description 38
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 25
- 239000010452 phosphate Substances 0.000 claims abstract description 25
- 238000012545 processing Methods 0.000 claims abstract description 10
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 66
- 230000007062 hydrolysis Effects 0.000 claims description 65
- 238000006460 hydrolysis reaction Methods 0.000 claims description 65
- 239000007789 gas Substances 0.000 claims description 57
- 238000006243 chemical reaction Methods 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 229910001868 water Inorganic materials 0.000 claims description 36
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 30
- 230000003472 neutralizing effect Effects 0.000 claims description 30
- 239000012071 phase Substances 0.000 claims description 27
- 230000035484 reaction time Effects 0.000 claims description 17
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 10
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003345 natural gas Substances 0.000 claims description 10
- CLUWOWRTHNNBBU-UHFFFAOYSA-N 3-methylthiopropanal Chemical compound CSCCC=O CLUWOWRTHNNBBU-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical group CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 claims description 2
- IKMGEAMKZUENRW-UHFFFAOYSA-N 2-methylsulfanylbutanoic acid Chemical compound CCC(SC)C(O)=O IKMGEAMKZUENRW-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 6
- 150000003863 ammonium salts Chemical class 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- -1 hydrogen cyanide Chemical compound 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 13
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 11
- 235000011130 ammonium sulphate Nutrition 0.000 description 11
- 239000012535 impurity Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 229930182817 methionine Natural products 0.000 description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 239000000039 congener Substances 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 235000019730 animal feed additive Nutrition 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 102000005262 Sulfatase Human genes 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000020776 essential amino acid Nutrition 0.000 description 1
- 239000003797 essential amino acid Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- FFXIGVUMVPUWDK-UHFFFAOYSA-N pentanethioamide Chemical compound CCCCC(N)=S FFXIGVUMVPUWDK-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- NBBJYMSMWIIQGU-UHFFFAOYSA-N propionic aldehyde Natural products CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 108060007951 sulfatase Proteins 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of method of clean continuous preparation 2-Hydroxy-4-methylthiobutyric acid, the preparation of preparation and 2-Hydroxy-4-methylthiobutyric acid including hydrogen cyanide, it is characterized by: the ammonium phosphate solution that the preparation of the hydrogen cyanide and the preparation of 2-Hydroxy-4-methylthiobutyric acid generate is handled in ammonia separation tower and ammonia refining tower, separates, recycles phosphoric acid and ammonia.Recycled for multiple times is carried out to ammonia and phosphoric acid during present invention process.Simplify largely discharge and processing step containing acid substance.Present invention process process is unique, the aqueous solution of phosphoric acid ammonium after extraction is pyrolyzed separation, hydrolysing step of the phosphate aqueous solution circulation for 2- 2-hydroxy-4-methylthio butyronitrile, raw material of the ammonia circulation for hydrogen cyanide preparation realizes environmentally protective, environmentally friendly cost reduction by 11.5%；Atom utilization of the present invention is high, and production cost reduces by 21.8%；The present invention does not generate ammonium salt byproduct, reduces sale and environmental protection pressure.
Description
Technical field
The invention belongs to the preparation method of chemical products, it is related to a kind of the clear of 2-Hydroxy-4-methylthiobutyric acid (HMBA)
Clean preparation method, belongs to technical field of chemical synthesis.
Background technique
2-Hydroxy-4-methylthiobutyric acid (HMBA/ liquid methionine) is typically considered the hydroxyl congener of methionine,
It is the congener of essential amino acid l-methionine.Methionine congener can effectively provide methionine as nutrition at
Point, especially as the additive of poultry feed.
HMBA in industrial production is racemic D, L mixture, preparation method be it is known, this method includes by first
Sulfenyl propionic aldehyde and hydrogen cyanide prepare 2- 2-hydroxy-4-methylthio butyronitrile, and in the presence of excessive inorganic acid, generally use sulfuric acid, make
The 2- 2-hydroxy-4-methylthio butyronitrile hydrolyzes to obtain 2-Hydroxy-4-methylthiobutyric acid.
HMBN is hydrolyzed using hydrochloric acid in US3773927A, obtains HMBA.Hydrolysis obtains the slurries containing solid ammonium chloride,
It is centrifugated ammonium chloride, the water being evaporated under reduced pressure in separating filtrate.If obtained ammonium chloride also needs further to locate as product
Reason.
CN85101573A is hydrolyzed using sulfuric acid, HMBN elder generation and sulfuric acid contact, and hydrolysis obtains the light color containing HMBA
Hydrolyzate, then, hydrolyzate contact in liquid-liquid system with solvent, and it includes to divide in the extract liquor of solvent that HMBA, which is transferred to,
From extract liquor and raffinate, steam distillation and extraction liquid removes solvent.The operation for controlling steamed fractional distillation column, makes to contain in the product of bottom
There are HMBA and water.
US3175000A uses sulfuric acid as hydrolysis medium, while using salting out after excess sulfuric acid ammonium is added, obtaining
HMBA.CN101006050, CN103664717 are also to be hydrolyzed using sulfuric acid, and CN104262216 equally uses sulphuric acid hydrolysis,
The water phase of solid ammonium salt is concentrated, crystallisation by cooling, is filtered, drying respectively obtains filtrate, solid ammonium salt.Solid ammonium salt does him and uses.
US4912257A is hydrolyzed using sulfuric acid one-step method, is not had to solvent, hydrolysis mixture is neutralized with ammonium hydroxide, mistake
The sulfuric acid of amount generates ammonium sulfate, is neutral sulfatase, and two obtained fluid phases separate respectively and are concentrated, obtain the MHA of liquid
With crystallinity ammonium sulfate.
But the above method can generate a large amount of waste sulfuric acid and ammonium sulfate, be to the processing step of these by-products in this way
It is required.It is that recycle all be a problem that processing for sulfur acid waste water, which is that processing heel row releases, and ammonium sulfate is come
It says, ammonium sulfate has been saturated in the market, meanwhile, if sold as product, need by a series of processing, processing cost
Income from sales can be higher than, this is not cost-effective for enterprise.And need to consume many energy in these processing steps,
Therefore the cost of preparation 2-Hydroxy-4-methylthiobutyric acid is increased.From the perspective of environmental protection, a large amount of ammonium sulfate is discharged
It is also undesirable with other acidic group salt.Therefore, for this problem, there are also Improvements for enterprise.
The method that 2-Hydroxy-4-methylthiobutyric acid is prepared in CN1223230A, including sulphuric acid hydrolysis cyanalcohol is used, generate master
Want the mixture of product HMBA and ammonium hydrogen sulfate and/or ammonium sulfate, separate HMBA, by the mixture of the containing sulfate after separating with
Aqueous solution form is converted to SO2 in the combustion furnace more than 800 DEG C, resulting to contain SO2Mixed gas it is molten in sulfuric acid
H is used in liquid2O2It is oxidized to H2SO4, the sulfuric acid recycled is again used in the hydrolysis of cyanalcohol.The method is by sulphur-containing substance
It all takes away burnings, increases the environmental protection treatment pressure of enterprise, while a large amount of burning the energy more than needing to consume.
The 2- hydroxyl-obtained to 2- hydroxy-4-(methylthio) base butyronitrile contact sulfuric acid is mentioned in CN1201031A and CN1336914A
A kind of mixed solution of ammonium hydrogen sulfate and ammonium sulfate is added in 4- methylthiobutanamide aqueous solution, it is existing that layering can occur rapidly
As, the water layer being layered can be recycled by the post-processing operation for crystallizing and filtering etc.The method is tested by experiment
The presence of card, ammonium sulfate only promotes layered effect, cannot replace real extractant, obtained ammonium sulfate and ammonium hydrogen sulfate
Solution still will carry out environmental protection treatment as waste water or other substances.
In conclusion following problems exist in the prior art:
(1) in the hydrolytic process of 2- 2-hydroxy-4-methylthio butyronitrile, it will use a large amount of inorganic acid, industry is raw at present
Multiselect sulfuric acid in production, can generate a large amount of ammonium sulfate, and the prior art is made after generally the by-product is burned or handled
It is sold for product, processing cost is excessively high.
(2) inorganic acid and ammonia therein are not fully used, and atom utilization is low.
Summary of the invention
The present invention is to solve the shortcomings of the prior art, and the present invention provides a kind of clean continuous preparation 2- hydroxyl -4-
The method of methylmercapto butyric acid.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:
A kind of method of clean continuous preparation 2-Hydroxy-4-methylthiobutyric acid, including hydrogen cyanide and 2- hydroxyl -4- first sulphur
The preparation of base butyric acid, which is characterized in that the ammonium phosphate solution of the preparation of hydrogen cyanide and the 2-Hydroxy-4-methylthiobutyric acid exists
It is handled in ammonia separation tower and ammonia refining tower, separates, recycles phosphoric acid and ammonia；It is returned by the ammonia for separating, recycling
It is reacted in hydrogen cyanide reactor.
Specifically, comprising the following steps:
(1) preparation of hydrogen cyanide:
Step a, the mixed gas I containing hydrogen cyanide is prepared
The mixed gas of air, natural gas and ammonia is passed through in hydrogen cyanide reactor, is carried out at 1000-1200 DEG C anti-
It answers, obtains the mixed gas I containing hydrogen cyanide；
In the mixed gas of the air, natural gas and ammonia, methane, ammonia, air molar ratio be 1:1~
1.04:5.5~6.
The molar ratio of the natural gas, is calculated with methane.
Step b, ammonia neutralizes
Mixed gas I is passed through ammonia neutralizing tower, is neutralized using phosphoric acid, II He of mixed gas not comprising ammonia is obtained
Aqueous solution containing ammonium phosphate；
The phosphoric acid is phosphate aqueous solution, and phosphoric acid is 0.01~0.1:1 with methane molar ratio described in step a.
The phosphate aqueous solution, concentration 15%-30%.
Above-mentioned ammonia neutralization temperature are as follows: 45-50 DEG C.
Step c, ammonia separation and ammonia refining
Aqueous solution containing ammonium phosphate is passed through the first ammonia separation tower, isolated phosphate aqueous solution and the mixing containing ammonia
Gas III；Mixed gas III is passed through the first ammonia refining tower D to handle, obtains ammonia and water.The isolated phosphoric acid
Set is neutralized for ammonia, and obtained ammonia recycle, which enters in hydrogen cyanide reactor, is reacted.
The first ammonia separation tower temperature degree is 180-220 DEG C, and tower bottom is passed through the steam of 2Mpa, reaction time 0.5-
0.7h；
The first ammonia separation tower temperature degree is preferably 180-200 DEG C；
The first ammonia refining tower temperature degree is 50-60 DEG C.
Step d, the successive reaction stage
When 2-Hydroxy-4-methylthiobutyric acid product discharge stablize after, regulating step a only need to be passed through NH3 make it is final
Methane in mixed gas, ammonia, air molar ratio be 1:0.01~0.05:5.5~6；The phosphoric acid that regulating step b is passed through
It only needs phosphoric acid total amount and the molar ratio of methane is 0.01-0.04:1.
(2) preparation of 2-Hydroxy-4-methylthiobutyric acid
Step a, 2- 2-hydroxy-4-methylthio butyronitrile is prepared
Mixed gas II obtained by the b step of step (1) is passed through in cyanalcohol reactor and is carried out with 3- methylthiopropionaldehyde
Reaction, obtains the aqueous solution of the butyronitrile of 2-hydroxy-4-methylthio containing 2-；
The molar ratio of methane described in a step of the 3- methylthiopropionaldehyde and step (1) is 1~1.05:1.
The preparation 2- 2-hydroxy-4-methylthio butyronitrile, 30-40 DEG C of reaction temperature, pressure 0.1-0.3MPa, time 6-8h.
Step b, it hydrolyzes
Above-mentioned 2- 2-hydroxy-4-methylthio butyronitrile solution is passed through in the first hydrolysis tower and the second hydrolysis tower and is hydrolyzed, is obtained
To the aqueous solution containing 2-Hydroxy-4-methylthiobutyric acid and ammonium phosphate；
Described is hydrolyzed to 2 one-step hydrolysis, and the first hydrolysis is hydrolyzed using phosphoric acid, and hydrolysis temperature is 50-60 DEG C, and hydrolysis makes
The molar ratio of methane described in a step of phosphoric acid and step (1) is 1~1.08:1；Second hydrolysis carries out water using water
Solution, hydrolysis temperature are as follows: 80-90 DEG C.
The phosphoric acid is phosphate aqueous solution, concentration 35%-55%.
Step c, extraction, distillation
Aqueous solution containing 2-Hydroxy-4-methylthiobutyric acid and ammonium phosphate is passed through extraction tower, extracted using extractant,
Organic phase comprising 2-Hydroxy-4-methylthiobutyric acid is passed through destilling tower, recycles extractant, obtain 2- hydroxyl -4- first sulphur by layering
Base butyric acid.
The extractant is methyl n-propyl ketone, methyl ethyl ketone, methyl amyl ketone, methyl isoamyl ketone, methyl-isobutyl
Ketone, ethyl butyl ketone, diisobutyl ketone, n-butanal, ethyl acetate, n-butyl acetate, n-propyl acetate, in isopropyl acetate
It is one or more；Extractant flow velocity is 10.2-12.6kg/h.
Step d, ammonium phosphate decomposes
By the raffinate phase after being layered in the step c of step (2), i.e. the aqueous solution comprising ammonium phosphate passes through filter, filtering
Impurity, then it is passed through the second ammonia separation tower K, isolated phosphate aqueous solution and the mixed gas IV comprising ammonia；The separation
Obtained phosphate aqueous solution is sent into the first hydrolysis tower.
The second ammonia separation tower: 180-220 DEG C of temperature；Tower bottom is passed through the steam of 2Mpa, reaction time 0.5-
0.8h。
The second ammonia separation tower: temperature is preferably 180-190 DEG C.
Step e, ammonia refining
Mixed gas IV comprising ammonia is passed through ammonia refining tower L to handle, obtains ammonia and water, ammonia returns to hydrogen cyanogen
It is reacted in acid reactor, water is sent into the second hydrolysis tower and participates in hydrolysis.
The temperature of second ammonia refining tower is as the temperature of the first ammonia refining tower.
Or
Mixed gas IV comprising ammonia is passed through ammonia refining tower D to handle, obtains ammonia.Described is isolated
Phosphate aqueous solution is sent into the first hydrolysis tower for hydrolyzing；Ammonia returns to be reacted in hydrogen cyanide reactor.
Step f, the successive reaction stage
After 2-Hydroxy-4-methylthiobutyric acid product discharge is stablized, the phosphoric acid that the b step of regulating step (2) is passed through only is needed
Phosphoric acid total amount and the molar ratio of methane are 1.01~1.1:1.
Main innovation point of the present invention is to recycle recycling after ammonium phosphate is pyrolyzed, it is preferred that emphasis is ammonia recycle is used for hydrogen cyanogen
The preparation of acid.
Compared with prior art, the invention has the advantages that:
(1) recycled for multiple times is carried out to ammonia and phosphoric acid during present invention process.Simplify largely containing the discharge of acid substance
And processing step.Present invention process process is unique, and the aqueous solution of phosphoric acid ammonium after extraction is pyrolyzed separation, phosphate aqueous solution circulation
For the hydrolysing step of 2- 2-hydroxy-4-methylthio butyronitrile, raw material of the ammonia circulation for hydrogen cyanide preparation realizes environmentally protective, ring
Guaranteed cost reduces by 11.5%；
(2) ammonia consumption is few.The present invention is by the excess of ammonia and 2- 2-hydroxy-4-methylthio fourth in hydrogen cyanide preparation process
The recovery ammonia that the aqueous solution pyrolysis of phosphoric acid ammonium obtains in acid preparation process, is recycled to hydrogen cyanide reactor, as hydrogen cyanide
Raw material, then in normal productive process, it is only necessary to add a small amount of ammonia.Atom utilization of the present invention is high, and production cost reduces
21.8%。
(3) present invention does not generate ammonium salt byproduct, reduces sale and environmental protection pressure.
Detailed description of the invention
Fig. 1 is the preparation flow figure of methionine described in embodiment 1-3；
Fig. 2 is the preparation flow figure of methionine described in embodiment 4-5；
In figure；
A-hydrogen cyanide reactor；B-ammonia neutralizing tower；C-the first ammonia separation tower；D-the first ammonia refining tower；E-cyanalcohol is anti-
Answer device；The first hydrolysis tower of F-；The second hydrolysis tower of G-；H-extraction tower；I-destilling tower；J-filter；The second ammonia separation of K-
Tower；L-the second ammonia refining tower.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described, it should be understood that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
A kind of method of clean continuous preparation 2-Hydroxy-4-methylthiobutyric acid of embodiment 1
The following steps are included:
(1) preparation of hydrogen cyanide
Step a, the mixed gas I containing hydrogen cyanide is prepared
According to iS-One method production technology, when device starts for the first time, filtered air is with 129.10kg/h and natural gas
It is sent into hydrogen cyanide reactor A feed pipe after mixing with 8.78kg/h, while being passed through the ammonia of 9.51kg/h, three to feed pipe
Mixed gas enters hydrogen cyanide reactor A, and reaction temperature is controlled at 1100 DEG C, and reaction is obtained containing hydrogen cyanide 8.51%, water 6.87%,
Ammonia 0.34%, carbon monoxide 0.87%, oxygen 1.89%, nitrogen 81.03%, the mixed gas I containing hydrogen cyanide of hydrogen 0.5%.
Step b, ammonia neutralizes
Mixed gas I containing hydrogen cyanide is sent into ammonia neutralizing tower B with the speed of 163.4kg/h, at the same ammonia neutralizing tower B tower top by
Ammonia neutralizing tower B is added with the flow velocity of 9.1kg/h in 15% phosphoric acid solution by microprocessor pump drive, and reaction temperature is controlled at 45 DEG C.In ammonia
It obtains with tower B tower top containing hydrogen cyanide 9.17%, carbon monoxide 0.94%, oxygen 2.04%, nitrogen 87.32%, the hydrogen cyanogen of hydrogen 0.54%
Sour mixed gas II, the solution containing 10.6% ammonium phosphate that tower bottom obtains are sent into the first ammonia separation tower with the flow velocity of 20.86kg/h
C。
Step c, ammonia separation and ammonia refining
First ammonia separation tower C temperature is controlled at 180 DEG C, and tower bottom is passed through the steam of 2Mpa, reaction time 0.5h, tower top
The first middle section ammonia refining tower D of mixed gas III (the ammonia, vapor) feeding that discharges；The discharging of first ammonia separation tower C tower bottom is 5%
The discharge nozzle of phosphate aqueous solution, the first ammonia separation tower C tower bottom merges with phosphoric acid feed pipe.Device run 64 hours after, only need to
Ammonia neutralizing tower B adds 30% phosphoric acid solution of 0.117kg/h, guarantee into ammonia neutralizing tower B phosphoric acid total amount and methane into
The molar ratio of material is 0.04:1.
First ammonia refining tower D tower top discharges material as the ammonia of 0.55kg/h, is sent into hydrogen cyanide reactor A, participates in reaction.
Tower bottom discharging waste water sends to burning, and the first ammonia refining tower D reaction temperature is controlled at 50 DEG C.
(2) preparation of 2-Hydroxy-4-methylthiobutyric acid
Step a, 2- 2-hydroxy-4-methylthio butyronitrile is prepared
3- methylthiopropionaldehyde is sent at the top of cyanalcohol reactor E with the speed of 53.56kg/h, while hydrogen cyanide mixed gas
II is fed with the speed of 151.63kg/h by the cyanalcohol bottom reactor E, and reaction temperature is 35 DEG C, reaction pressure 0.128MPa,
Reaction time 8h, the discharging of cyanalcohol reactor E tower bottom are the aqueous solution of the butyronitrile of 2-hydroxy-4-methylthio containing 2-.
Step b, it hydrolyzes
The aqueous solution of the butyronitrile of 2-hydroxy-4-methylthio containing 2- is sent into the first hydrolysis tower F with the speed of 67.6kg/h, tower top with
The phosphoric acid solution that concentration is 30% is added in the speed of 168.23kg/h, and the control of the first hydrolysis tower F temperature at 55 DEG C, send by tower bottom discharging
Enter the second middle section hydrolysis tower G.Meanwhile second hydrolysis tower G tower top with 9.27kg/h speed be added process water, reaction temperature control exists
85℃.Second hydrolysis tower G tower bottom discharge material be containing 12.13% 2-Hydroxy-4-methylthiobutyric acid, 5.48% ammonium phosphate it is mixed
Heshui solution, is sent directly into extraction tower H, and 2-Hydroxy-4-methylthiobutyric acid yield is up to 97.5%.
Above-mentioned yield is calculating after having hydrolyzed, is calculated based on 2- hydroxy-4-(methylthio) base butyronitrile (cyanalcohol).
Step c, extraction, distillation
Extractant methyl ethyl ketone is passed through extraction tower H tower top with the speed of 10.2kg/h simultaneously, discharges with the second hydrolysis tower G tower bottom
It is layered in extraction tower H after material mixing, upper layer extraction phase is organic phase, includes 2-Hydroxy-4-methylthiobutyric acid, methyl ethyl ketone；
Raffinate phase is water phase, includes ammonium phosphate, water, impurity.
Extraction phase is sent into destilling tower I, and destilling tower I tower top steams methyl ethyl ketone and is sent into the recycling of extractant feed pipe.Tower bottom
Product is the 2-Hydroxy-4-methylthiobutyric acid aqueous solution of content 88.05%.
Step d, ammonium phosphate decomposes
Raffinate phase is through filter J, and impurity, which is sent into, to be burned, and filtrate is the ammonium phosphate solution containing 6.24%, is sent into the second ammonia point
From tower K, tower bottom is passed through the steam of 2Mpa, reaction time 0.5h, and the second ammonia separation tower K temperature is controlled at 185 DEG C, second
Ammonia separation tower K tower bottom is 3.47% phosphate aqueous solution of 502.48kg/h, is sent into the first hydrolysis tower F and is recycled.
Step e, ammonia refining
The second ammonia refining tower L is sent into the discharging of second ammonia separation tower K tower top.Second ammonia refining tower L tower top obtains 7.21kg/h
Ammonia, be sent into hydrogen cyanide reactor A used as raw material.The water that the discharging of second ammonia refining tower L tower bottom is 50.32kg/h, send
Enter the second hydrolysis tower G, participates in hydrolysis.
After device is run 64 hours, the charging of hydrogen cyanide reactor A only needs to add to hydrogen cyanide reactor A ammonia feed mouth
Ammonia 1.34kg/h, guarantee final charging ammonia: methane molar ratio is 1.04:1.
A kind of method of clean continuous preparation 2-Hydroxy-4-methylthiobutyric acid of embodiment 2
The following steps are included:
(1) preparation of hydrogen cyanide
Step a, the mixed gas I containing hydrogen cyanide is prepared
According to iS-One method production technology, when device starts for the first time, filtered air is with 143.21kg/h and natural gas
It is sent into hydrogen cyanide reactor A feed pipe after mixing with 9.74kg/h, while being passed through the ammonia of 10.55kg/h, three to feed pipe
Mixed gas enters hydrogen cyanide reactor A, and reaction temperature is controlled at 1050 DEG C, and reaction is obtained containing hydrogen cyanide 8.86%, water 6.67%,
Ammonia 0.44%, carbon monoxide 0.77%, oxygen 1.29%, nitrogen 81.47%, the hydrogen cyanide mixed gas I of hydrogen 0.5%.
Step b, ammonia neutralizes
Hydrogen cyanide mixed gas I is sent into ammonia neutralizing tower B with the speed of 187.5kg/h.Ammonia neutralizing tower B tower top is by liquid simultaneously
Ammonia neutralizing tower B is added with the flow velocity of 10.2kg/h in 20% phosphoric acid solution by metering pump, and reaction temperature is controlled at 45 DEG C.Ammonia neutralizes
Tower B tower top is obtained containing hydrogen cyanide 9.54%, carbon monoxide 0.83%, oxygen 1.39%, nitrogen 87.71%, the hydrogen cyanide of hydrogen 0.54%
Mixed gas II, the solution containing 13.96% ammonium phosphate that tower bottom obtains is with feeding the first ammonia separation tower C of 23.53kg/h.
Step c, ammonia separation and ammonia refining
First ammonia separation tower C temperature is controlled at 185 DEG C, and tower bottom is passed through the steam of 2Mpa, reaction time 0.6h, tower top
The first middle section ammonia refining tower D of mixed gas III (the ammonia, vapor) feeding that discharges；First ammonia separation tower C tower bottom discharges
11.58% phosphate aqueous solution, discharge nozzle merge with phosphoric acid feed pipe.It, only need to be to ammonia neutralizing tower B after device operation 48 as a child
Add 30% phosphoric acid solution of 0.017kg/h.Guarantee mole of the phosphoric acid total amount and methane feed into ammonia neutralizing tower B
Than for 0.03:1.
The ammonia that the discharging of first ammonia refining tower D tower top is 0.82kg/h, is sent into hydrogen cyanide reactor A, participates in reaction.Tower bottom
Discharging waste water sends to burning.First ammonia refining tower D reaction temperature is controlled at 55 DEG C.
(2) preparation of 2-Hydroxy-4-methylthiobutyric acid
Step a, 2- 2-hydroxy-4-methylthio butyronitrile is prepared
3- methylthiopropionaldehyde is sent at the top of cyanalcohol reactor E with the speed of 63.99kg/h, while hydrogen cyanide mixed gas
II is fed with the speed of 174.17kg/h by the cyanalcohol bottom reactor E, and reaction temperature is 40 DEG C, reaction pressure 0.28MPa, instead
Residence time 6h is answered, the discharging of cyanalcohol reactor E tower bottom is the solution of the 2- 2-hydroxy-4-methylthio butyronitrile containing 99.8%.
Step b, it hydrolyzes
Solution containing 99.8% 2- 2-hydroxy-4-methylthio butyronitrile is sent into the first hydrolysis tower F, tower with the speed of 80.76kg/h
The phosphoric acid solution that concentration is 50% is added with the speed of 200.99kg/h for top, and the first hydrolysis tower F temperature is controlled at 50 DEG C, and tower bottom goes out
Material is sent into the second middle section hydrolysis tower G.Process water, the second hydrolysis tower G reaction temperature is added with 11.075kg/h speed in tower top simultaneously
Control is at 80 DEG C；Second hydrolysis tower G tower bottom discharges material as the 2-Hydroxy-4-methylthiobutyric acid containing 12.13%, 5.48% phosphoric acid
The mixed aqueous solution of ammonium is sent directly into extraction tower H.2-Hydroxy-4-methylthiobutyric acid yield is up to 96.98%.
Above-mentioned yield is calculating after having hydrolyzed, is calculated based on 2- hydroxy-4-(methylthio) base butyronitrile (cyanalcohol).
Step c, extraction, distillation
Extractant ethyl acetate is passed through extraction tower H tower top with the speed of 11.8kg/h, goes out material with the second hydrolysis tower G tower bottom
It is layered in extraction tower H after material mixing, upper layer extraction phase is that organic phase includes 2-Hydroxy-4-methylthiobutyric acid, methyl ethyl ketone；Raffinate
It include mutually ammonium phosphate, water, impurity for water phase.
To be sent into destilling tower I, destilling tower I tower top steams methyl ethyl ketone and is sent into the recycling of extractant feed pipe extraction phase.Tower
Bottom product is the 2-Hydroxy-4-methylthiobutyric acid aqueous solution of content 88.42%.
Step d, ammonium phosphate decomposes
Through filter J, impurity is sent into be burned raffinate phase, and filtrate is to be sent into the second ammonia separation containing 6.34% ammonium phosphate solution
Tower K, tower bottom are passed through the steam of 2Mpa, reaction time 0.6h, and the control of the second ammonia separation tower K temperature is at 180 DEG C, the second ammonia
Knockout tower K tower bottom is 3.02% phosphate aqueous solution of 660.47kg/h, is sent into the first hydrolysis tower F and is recycled.
Step e, ammonia refining
The second ammonia refining tower L is sent into the discharging of second ammonia separation tower K tower top.Second ammonia refining tower L tower top obtains 8.61kg/h
Ammonia, be sent into hydrogen cyanide reactor A used as raw material.The water that tower bottom discharging is 154.71kg/h, is sent into the second hydrolysis tower
G participates in hydrolysis.
After device is run 48 hours, the charging of hydrogen cyanide reactor A only needs to add to hydrogen cyanide reactor A ammonia feed mouth
Ammonia 1.44kg/h, guarantee final charging ammonia: methane molar ratio is 1.03:1.
A kind of method of clean continuous preparation 2-Hydroxy-4-methylthiobutyric acid of embodiment 3
The following steps are included:
(1) preparation of hydrogen cyanide
Step a, the mixed gas I containing hydrogen cyanide is prepared
According to iS-One method production technology, when device starts for the first time filtered air with 162.08kg/h and natural gas with
It is sent into hydrogen cyanide reactor A feed pipe after 11.03kg/h mixing, while being passed through the ammonia of 11.94kg/h, three to feed pipe
Mixed gas enters hydrogen cyanide reactor A, and reaction temperature is controlled at 1000 DEG C, and reaction is obtained containing hydrogen cyanide 8.91%, water 6.62%,
Ammonia 0.42%, carbon monoxide 0.66%, oxygen 1.31%, nitrogen 81.68%, the hydrogen cyanide mixed gas I of hydrogen 0.4%.
Step b, ammonia neutralizes
Hydrogen cyanide mixed gas I is sent into ammonia neutralizing tower B with the speed of 205.8kg/h.Ammonia neutralizing tower B tower top is by liquid simultaneously
Ammonia neutralizing tower B is added with 9.8kg/h in 25% phosphoric acid solution by metering pump, and reaction temperature is controlled at 50 DEG C.Ammonia neutralizing tower B tower top
It obtains containing hydrogen cyanide 9.58%, carbon monoxide 0.71%, oxygen 1.41%, nitrogen 87.87%, the hydrogen cyanide gaseous mixture of hydrogen 0.43%
Body II, the solution containing 14.17% ammonium phosphate that tower bottom obtains are sent into the first ammonia separation tower C with the flow velocity of 24.29kg/h.
Step c, ammonia separation and ammonia refining
First ammonia separation tower C temperature is controlled at 190 DEG C, and tower bottom is passed through the steam of 2Mpa, reaction time 0.7h, tower top
The first middle section ammonia refining tower D of mixed gas III (the ammonia, vapor) feeding that discharges；First ammonia separation tower C tower bottom discharges
12.08% phosphate aqueous solution merges with phosphoric acid feed pipe.After device is run 72 hours, it need to only be added to ammonia neutralizing tower B
30% phosphoric acid solution of 0.018kg/h guarantees that the molar ratio of the phosphoric acid total amount and methane feed that enter ammonia neutralizing tower B is
0.03:1.
The ammonia that the discharging of first ammonia refining tower D tower top is 0.86kg/h, is sent into hydrogen cyanide reactor A, participates in reaction.Tower bottom
Discharging waste water sends to burning.First ammonia refining tower D reaction temperature is controlled at 50 DEG C.
(2) preparation of 2-Hydroxy-4-methylthiobutyric acid
Step a, 2- 2-hydroxy-4-methylthio butyronitrile is prepared
3- methylthiopropionaldehyde is sent at the top of cyanalcohol reactor E with the speed of 70.63kg/h, while hydrogen cyanide gaseous mixture
Body II is fed with the speed of 191.31kg/h by the cyanalcohol bottom reactor E, and reaction temperature is 30 DEG C, reaction pressure 0.1MPa,
Reaction time 6h, the discharging of cyanalcohol reactor E tower bottom are the solution of the 2- 2-hydroxy-4-methylthio butyronitrile containing 99.9%.
Step b, it hydrolyzes
Solution containing 99.9% 2- 2-hydroxy-4-methylthio butyronitrile is sent into the first hydrolysis tower F, tower with the speed of 89.05kg/h
The phosphoric acid solution that concentration is 45% is added with the speed of 221.85kg/h for top, and the first hydrolysis tower F temperature is controlled at 60 DEG C, and tower bottom goes out
Material is sent into the second middle section hydrolysis tower G, while process water, the second hydrolysis tower G reaction temperature control is added with 12.22kg/h speed in tower top
System is at 90 DEG C；Second hydrolysis tower G tower bottom discharges material as the 2-Hydroxy-4-methylthiobutyric acid containing 12.25%, 5.23% ammonium phosphate
Mixed aqueous solution be sent directly into extraction tower H.2-Hydroxy-4-methylthiobutyric acid yield is up to 97.21%.
Above-mentioned yield is calculating after having hydrolyzed, is calculated based on 2- hydroxy-4-(methylthio) base butyronitrile (cyanalcohol).
Step c, extraction, distillation
Extractant n-butanal is passed through extraction tower H tower top with the speed of 12.6kg/h, with the second hydrolysis tower G tower bottom discharging material
It is layered in extraction tower H after mixing, upper layer extraction phase is that organic phase includes 2-Hydroxy-4-methylthiobutyric acid, n-butanal；Raffinate phase
It include ammonium phosphate, water, impurity for water phase.
Extraction phase is sent into destilling tower I, and destilling tower I tower top steams n-butanal and is sent into the recycling of extractant feed pipe.Tower bottom
Product is the 2-Hydroxy-4-methylthiobutyric acid aqueous solution of content 89.39%.
Step d, ammonium phosphate decomposes
Through filter J, impurity is sent into be burned raffinate phase, and filtrate is to be sent into the second ammonia separation containing 6.25% ammonium phosphate solution
Tower K, tower bottom are passed through the steam of 2Mpa, and reaction time 0.8h, at 190 DEG C, the second ammonia divides the control of the second ammonia separation tower K temperature
From 3.02% phosphate aqueous solution that tower K tower bottom is 728.97kg/h, it is sent into the first hydrolysis tower F and is recycled.
Step e, ammonia refining
The second ammonia refining tower L is sent into the discharging of second ammonia separation tower K tower top.Second ammonia refining tower L tower top obtains 9.51kg/h
Ammonia, be sent into hydrogen cyanide reactor A used as raw material.The water that tower bottom discharging is 221.11kg/h, is sent into the second hydrolysis tower
G participates in hydrolysis.
After device is run 72 hours, the charging of hydrogen cyanide reactor A only needs to add to hydrogen cyanide reactor A ammonia feed mouth
Ammonia 1.637kg/h.Guarantee final charging ammonia: methane molar ratio is 1.02:1.
The temperature of the second ammonia refining tower L is the same with the temperature of the first ammonia refining tower D in embodiment 1-3.
A kind of method of clean continuous preparation 2-Hydroxy-4-methylthiobutyric acid of embodiment 4
The following steps are included:
(1) preparation of hydrogen cyanide
Step a, the mixed gas I containing hydrogen cyanide is prepared
According to iS-One method production technology, when device starts for the first time, filtered air is with 129.10kg/h and natural gas
It is sent into hydrogen cyanide reactor A feed pipe after mixing with 8.61kg/h, while being passed through the ammonia of 9.51kg/h to feed pipe, three is mixed
It closes gas and enters hydrogen cyanide reactor A, reaction temperature is controlled at 1100 DEG C, and reaction is obtained containing hydrogen cyanide 8.51%, water 6.87%, ammonia
Gas 0.34%, carbon monoxide 0.87%, oxygen 1.89%, nitrogen 81.03%, the hydrogen cyanide mixed gas I of hydrogen 0.5%.
Step b, ammonia neutralizes
Hydrogen cyanide mixed gas I is sent into ammonia neutralizing tower B with the speed of 163.4kg/h.Ammonia neutralizing tower B tower top is by liquid simultaneously
Ammonia neutralizing tower B is added with 9.1kg/h in 30% phosphoric acid solution by metering pump, and reaction temperature is controlled at 45 DEG C.Ammonia neutralizing tower B tower top
It obtains containing hydrogen cyanide 9.17%, carbon monoxide 0.94%, oxygen 2.04%, nitrogen 87.32%, the hydrogen cyanide gaseous mixture of hydrogen 0.54%
Body II, the solution containing 10.6% ammonium phosphate that tower bottom obtains are sent into the first ammonia separation tower C with the flow velocity of 20.86kg/h.
Step c, ammonia separation and ammonia refining
First ammonia separation tower C temperature is controlled at 200 DEG C, and tower bottom is passed through the steam of 2Mpa, reaction time 0.7h, tower top
The first middle section ammonia refining tower D of mixed gas III (the ammonia, vapor) feeding that discharges；First ammonia separation tower C tower bottom discharges
13.06% phosphate aqueous solution, discharge nozzle merge with phosphoric acid feed pipe.After device is run 48 hours, it need to only be mended to ammonia neutralizing tower B
Add 30% phosphoric acid solution of 0.017kg/h, guarantees the molar ratio of the phosphoric acid total amount and methane feed into ammonia neutralizing tower B
For 0.02:1.
(2) preparation of 2-Hydroxy-4-methylthiobutyric acid
Step a, 2- 2-hydroxy-4-methylthio butyronitrile is prepared
3- methylthiopropionaldehyde is sent at the top of cyanalcohol reactor E with the speed of 53.56kg/h, while hydrogen cyanide mixed gas
II is fed with the speed of 151.63kg/h by the cyanalcohol bottom reactor E, and reaction temperature is 35 DEG C, reaction pressure 0.128MPa,
Reaction time 8h, cyanalcohol reactor E tower bottom discharging material are the solution of the 2- 2-hydroxy-4-methylthio butyronitrile containing 99%.
Step b, it hydrolyzes
Solution containing 99% 2- 2-hydroxy-4-methylthio butyronitrile is sent into the first hydrolysis tower F, tower top with the speed of 67.6kg/h
The phosphoric acid solution that concentration is 50% is added with the speed of 168.23kg/h, at 60 DEG C, tower bottom discharges the control of the first hydrolysis tower F temperature
It is sent into the second middle section hydrolysis tower G, while process water is added with 9.27kg/h speed in tower top；Second hydrolysis tower G tower bottom discharging material
For the 2-Hydroxy-4-methylthiobutyric acid containing 12.13%, the mixed aqueous solution of 5.48% ammonium phosphate is sent directly into extraction tower H.The
Two hydrolysis tower G reaction temperatures are controlled at 90 DEG C.2-Hydroxy-4-methylthiobutyric acid yield is up to 97.06%.
Above-mentioned yield is calculating after having hydrolyzed, is calculated based on 2- hydroxy-4-(methylthio) base butyronitrile (cyanalcohol).
Step c, extraction, distillation
Extractant methyl ethyl ketone is passed through extraction tower H tower top with the speed of 10.2kg/h, with the discharging mixing of the second hydrolysis tower G tower bottom
It is layered in extraction tower H afterwards, upper layer extraction phase is that organic phase includes 2-Hydroxy-4-methylthiobutyric acid, methyl ethyl ketone；Raffinate phase is water
It mutually include ammonium phosphate, water, impurity.
To be sent into destilling tower I, destilling tower I tower top steams methyl ethyl ketone and is sent into the recycling of extractant feed pipe extraction phase.Tower
Bottom product is the 2-Hydroxy-4-methylthiobutyric acid aqueous solution of content 88.05%.
Step d, ammonium phosphate decomposes
Through filter J, impurity is sent into be burned raffinate phase, and filtrate is to be sent into the second ammonia separation containing 6.24% ammonium phosphate solution
Tower K, tower bottom are passed through the steam of 2Mpa, reaction time 0.5h, and the control of the second ammonia separation tower K temperature is at 185 DEG C, the second ammonia
Knockout tower K tower bottom is 3.47% phosphate aqueous solution of 502.48kg/h, is sent into the first hydrolysis tower F and is recycled.
Step e, ammonia refining
The first ammonia refining tower D is sent into the discharging of second ammonia separation tower K tower top.
First ammonia refining tower D tower top obtains the ammonia of 7.76kg/h, is sent into hydrogen cyanide reactor A and uses as raw material.The
Burning is sent in the discharging of one ammonia refining tower D tower bottom.The water that the discharging of second ammonia separation tower K tower bottom is 50.32kg/h is sent into the first hydrolysis
Tower F participates in hydrolysis.After device is stable, hydrogen cyanide reactor A charging only need to hydrogen cyanide reactor A ammonia into
Material mouth adds ammonia 1.34kg/h, and guarantee final charging ammonia: methane molar ratio is 1.02:1.
The temperature of first ammonia refining tower D is 50 DEG C；
After device is run 48 hours, product is 87.95% 2-Hydroxy-4-methylthiobutyric acid aqueous solution, can directly be used
In animal feed additive.
A kind of method of clean continuous preparation 2-Hydroxy-4-methylthiobutyric acid of embodiment 5
The following steps are included:
(1) preparation of hydrogen cyanide
Step a, the mixed gas I containing hydrogen cyanide is prepared
According to iS-One method production technology, when device starts for the first time, filtered air is with 155.53kg/h and natural gas
It is sent into hydrogen cyanide reactor A feed pipe after mixing with 10.37kg/h, while being passed through the ammonia of 11.46kg/h to feed pipe, three
Person's mixed gas enters hydrogen cyanide reactor A, and reaction temperature is controlled at 1100 DEG C, and reaction is obtained containing hydrogen cyanide 8.81%, water
6.72%, ammonia 0.41%, carbon monoxide 0.67%, oxygen 1.42%, nitrogen 81.57%, the hydrogen cyanide mixed gas I of hydrogen 0.4%.
Step b, ammonia neutralizes
Hydrogen cyanide mixed gas I is sent into ammonia neutralizing tower B with the speed of 198.6kg/h.Ammonia neutralizing tower B tower top is by liquid simultaneously
Ammonia neutralizing tower B is added with the flow velocity of 9.8kg/h in 30% phosphoric acid solution by metering pump, and reaction temperature is controlled at 45 DEG C.Ammonia neutralizing tower
B tower top is obtained containing hydrogen cyanide 9.49%, carbon monoxide 0.72%, oxygen 1.53%, nitrogen 87.83%, and the hydrogen cyanide of hydrogen 0.43% is mixed
Gas II is closed, the solution containing 13.53% ammonium phosphate that tower bottom obtains is with feeding the first ammonia separation tower C of 23.96kg/h.
Step c, ammonia separation and ammonia refining
The control of first ammonia separation tower C temperature is at 190 DEG C, and tower bottom is passed through the steam of 2Mpa, reaction time 0.7h, the
The first middle section ammonia refining tower D is sent into one ammonia separation tower C tower top discharging mixed gas III (ammonia, vapor)；First ammonia separation tower C
The phosphate aqueous solution that tower bottom discharging is 12.25%, merges with phosphoric acid feed pipe.It, only need to be into ammonia after device stable operation 64 hours
It adds 30% phosphoric acid solution of 0.017kg/h with tower B, guarantees phosphoric acid total amount and methane feed into ammonia neutralizing tower B
Molar ratio is 0.02:1.
(2) preparation of 2-Hydroxy-4-methylthiobutyric acid
Step a, 2- 2-hydroxy-4-methylthio butyronitrile is prepared
3- methylthiopropionaldehyde is sent at the top of cyanalcohol reactor E with the speed of 67.39kg/h, while hydrogen cyanide mixed gas
II is fed with the speed of 184.44kg/h by the cyanalcohol bottom reactor E, and reaction temperature is 38 DEG C, reaction pressure 0.3MPa, instead
Residence time 6h is answered, cyanalcohol reactor E tower bottom discharging material is the solution of the 2- 2-hydroxy-4-methylthio butyronitrile containing 99.9%.
Step b, it hydrolyzes
Solution containing 99.9% 2- 2-hydroxy-4-methylthio butyronitrile is sent into the first hydrolysis tower F, tower with the speed of 84.97kg/h
Top is added the phosphoric acid solution that concentration is 30% with the speed of 211.69kg/h, and the control of the first hydrolysis tower F temperature is at 55 DEG C, the first water
It solves the discharging of tower F tower bottom and is sent into the second middle section hydrolysis tower G, while process water is added with 11.67kg/h speed in tower top；Second hydrolysis tower
G tower bottom discharges material as the 2-Hydroxy-4-methylthiobutyric acid containing 12.12%, and the mixed aqueous solution of 5.49% ammonium phosphate is directly sent
Enter extraction tower H, the control of the second hydrolysis tower G reaction temperature is at 85 DEG C, and 2-Hydroxy-4-methylthiobutyric acid yield is up to 97.55%.
Above-mentioned yield is calculating after having hydrolyzed, is calculated based on 2- hydroxy-4-(methylthio) base butyronitrile (cyanalcohol).
Step c, extraction, distillation
Extractant methyl n-propyl ketone is passed through extraction tower H tower top with the speed of 11.5kg/h, goes out with the second hydrolysis tower G tower bottom
It is layered in extraction tower H after material mixing, upper layer extraction phase is the organic phase comprising 2-Hydroxy-4-methylthiobutyric acid, methyl positive third
Base ketone；Raffinate phase be include ammonium phosphate, water, the water phase of impurity.
Extraction phase is sent into destilling tower I, and destilling tower I tower top, which steams methyl n-propyl ketone, which is sent into extractant feed pipe circulation, makes
With.Tower bottom product is the 2-Hydroxy-4-methylthiobutyric acid aqueous solution of content 89.19%.
Step d, ammonium phosphate decomposes
Through filter J, impurity is sent into be burned raffinate phase, and filtrate is to be sent into the second ammonia separation containing 6.25% ammonium phosphate solution
Tower K, tower bottom are passed through the steam of 2Mpa, and reaction time 0.5h, at 185 DEG C, the second ammonia divides the control of the second ammonia separation tower K temperature
From 4.37% phosphate aqueous solution that tower K tower bottom is 506.84kg/h, it is sent into the first hydrolysis tower F and is recycled.
Step e, ammonia refining
Second, which decomposes column overhead discharging, is sent into the first ammonia refining tower D.
First ammonia refining tower D tower top obtains the ammonia of 9.88kg/h, is sent into hydrogen cyanide reactor A and uses as raw material.The
Burning is sent in the discharging of one ammonia refining tower D tower bottom.After device is stable, the charging of hydrogen cyanide reactor A only needs anti-to hydrogen cyanide
Device A ammonia feed mouth is answered to add ammonia 1.57kg/h.
After device is run 64 hours, product is 88.96% 2-Hydroxy-4-methylthiobutyric acid aqueous solution, can directly be used
In animal feed additive.
The temperature of first ammonia refining tower D is 60 DEG C.
Unless specifically indicated, the ratio that the present invention uses is mass ratio, and the percentage of use is quality percentage
Than.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (9)
1. a kind of method of clean continuous preparation 2-Hydroxy-4-methylthiobutyric acid, preparation and 2- hydroxyl -4- including hydrogen cyanide
The preparation of methylmercapto butyric acid, it is characterised in that: the preparation of the hydrogen cyanide and the preparation of 2-Hydroxy-4-methylthiobutyric acid generate
Ammonium phosphate solution handled in ammonia separation tower and ammonia refining tower, separate, recycle phosphoric acid and ammonia；
The preparation of the 2-Hydroxy-4-methylthiobutyric acid, including ammonium phosphate decomposes and ammonia refining；The ammonium phosphate decomposes, by phosphorus
Sour aqueous ammonium is passed through the second ammonia separation tower, isolated phosphate aqueous solution and the mixed gas IV comprising ammonia；Point
The first hydrolysis tower is sent into from obtained phosphate aqueous solution；
Mixed gas IV comprising ammonia is passed through the second ammonia refining tower and handled, obtains ammonia and water by the ammonia refining；Or
Mixed gas IV comprising ammonia is passed through the first ammonia refining tower to handle, obtains ammonia and water.
2. the method for the clean continuous preparation 2-Hydroxy-4-methylthiobutyric acid of one kind according to claim 1, feature exist
In:
It returns in hydrogen cyanide reactor and is reacted by the ammonia for separating, recycling.
3. the method for the clean continuous preparation 2-Hydroxy-4-methylthiobutyric acid of one kind according to claim 1, feature exist
In: the preparation of the hydrogen cyanide, including successive reaction stage；The successive reaction stage, adjust NH3 in the preparation of hydrogen cyanide
Intake, so that the molar ratio of methane in final mixed gas, ammonia, air is 1:0.01~0.05:5.5~6；Adjust ammonia
The phosphate aqueous solution amount being passed through in neutralization procedure, so that phosphoric acid total amount and the molar ratio of methane are 0.01~0.04:1；The 2-
The preparation of hydroxy-4-methylthiobutyric acid, including successive reaction stage；The successive reaction stage adjusts and is passed through in hydrolysing step
Phosphate aqueous solution amount so that phosphoric acid total amount and the molar ratio of methane are 1.01~1.1:1.
4. the method for the clean continuous preparation 2-Hydroxy-4-methylthiobutyric acid of one kind according to claim 1, feature exist
In:
The preparation of the hydrogen cyanide, including ammonia separation and ammonia refining, the ammonia separation and ammonia refining, ammonium phosphate solution is passed through
First ammonia separation tower, isolated phosphoric acid and the mixed gas III containing ammonia；By mixed gas III be passed through the first ammonia refining tower into
Row processing, obtains ammonia.
5. the method for the clean continuous preparation 2-Hydroxy-4-methylthiobutyric acid of one kind according to claim 4, feature exist
In: the first ammonia separation tower temperature degree is 180-220 DEG C, and tower bottom is passed through the steam of 2Mpa, reaction time 0.5-0.7h；Institute
Stating the first ammonia refining tower temperature degree is 50-60 DEG C.
6. the method for the clean continuous preparation 2-Hydroxy-4-methylthiobutyric acid of one kind according to claim 1, feature exist
In: the second ammonia separation tower: 180-220 DEG C of temperature；Tower bottom is passed through the steam of 2Mpa, reaction time 0.5-0.8h.
7. the method for the clean continuous preparation 2-Hydroxy-4-methylthiobutyric acid of one kind according to claim 1, feature exist
In: the second ammonia refining tower temperature degree is 50-60 DEG C.
8. the method for the clean continuous preparation 2-Hydroxy-4-methylthiobutyric acid of one kind according to claim 1, feature exist
In:
The preparation of the hydrogen cyanide, further comprising the steps of:
A, the mixed gas I containing hydrogen cyanide is prepared
The mixed gas of air, natural gas and ammonia is passed through in hydrogen cyanide reactor, is reacted at 1000-1200 DEG C,
Obtain the mixed gas I containing hydrogen cyanide；
In the mixed gas of the air, natural gas and ammonia, methane, ammonia, air molar ratio be 1:1~1.04:5.5
~6；
B, ammonia neutralizes
Mixed gas I is passed through ammonia neutralizing tower, is neutralized using phosphoric acid, the mixed gas II not comprising ammonia is obtained and is contained
The aqueous solution of ammonium phosphate；
The phosphoric acid is phosphate aqueous solution, and phosphoric acid and methane molar ratio are 0.01~0.1:1；
The phosphate aqueous solution, concentration 15%-30%；
The ammonia neutralization temperature are as follows: 45-50 DEG C.
9. the method for the clean continuous preparation 2-Hydroxy-4-methylthiobutyric acid of one kind according to claim 8, feature exist
In:
The preparation of the 2-Hydroxy-4-methylthiobutyric acid, further comprising the steps of:
A, 2- 2-hydroxy-4-methylthio butyronitrile is prepared
Mixed gas II is passed through in cyanalcohol reactor and is reacted with 3- methylthiopropionaldehyde, 2-hydroxy-4-methylthio containing 2- is obtained
The aqueous solution of butyronitrile；
The molar ratio of the 3- methylthiopropionaldehyde and methane is 1~1.05:1；
The preparation 2- 2-hydroxy-4-methylthio butyronitrile, 30-40 DEG C of reaction temperature, pressure 0.1-0.3MPa, time 6-8h；
B, it hydrolyzes
Above-mentioned 2- 2-hydroxy-4-methylthio butyronitrile solution is passed through in the first hydrolysis tower and the second hydrolysis tower and is hydrolyzed, is contained
The aqueous solution of 2-Hydroxy-4-methylthiobutyric acid and ammonium phosphate；
C, extraction, distillation
Aqueous solution containing 2-Hydroxy-4-methylthiobutyric acid and ammonium phosphate is passed through extraction tower, extracted, divided using extractant
Organic phase comprising 2-Hydroxy-4-methylthiobutyric acid is passed through destilling tower, recycles extractant, obtain 2- 2-hydroxy-4-methylthio by layer
Butyric acid；Raffinate phase is the aqueous solution of phosphoric acid ammonium；
The extractant is methyl n-propyl ketone, methyl ethyl ketone, methyl amyl ketone, methyl isoamyl ketone, methyl iso-butyl ketone (MIBK), second
One of base butyl ketone, diisobutyl ketone, n-butanal, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate
Or it is a variety of.
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| CN103664717A (en) * | 2013-11-19 | 2014-03-26 | 重庆紫光化工股份有限公司 | Preparation method of cheap and environmentally friendly D, L-2- hydroxyl-4-methylthio butyric acid |
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| GB1080667A (en) * | 1964-07-28 | 1967-08-23 | Chemical And Phosphates Ltd | Process for the preparation of salts of ª‡-hydroxy-ª†-lower alkylmercapto butyric acids |
| US4419198A (en) * | 1981-06-22 | 1983-12-06 | Monsanto Company | Purification of methioine hydroxy analogue hydrolyzate by electrodialysis |
| CN101264901A (en) * | 2008-04-29 | 2008-09-17 | 石家庄工大化工设备有限公司 | Ammonia recovery method for gas mixture in hydrogen cyanide production |
| CN102730720A (en) * | 2011-04-14 | 2012-10-17 | 重庆紫光化工股份有限公司 | Method and system for recovering ammonia from gas containing hydrocyanic acid |
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Application publication date: 20180126 Assignee: Ningbo Zhenhai Refining and Chemical Xinhecheng Biotechnology Co.,Ltd. Assignor: SHANDONG XINHECHENG AMINO ACID Co.,Ltd. Contract record no.: X2024980000380 Denomination of invention: A clean and continuous method for preparing 2-hydroxy-4-methylthiobutyric acid Granted publication date: 20190604 License type: Common License Record date: 20240115 |