CN1030747A - Cane molasses is produced the industrial ethanedioic acid method - Google Patents
Cane molasses is produced the industrial ethanedioic acid method Download PDFInfo
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- CN1030747A CN1030747A CN 87104737 CN87104737A CN1030747A CN 1030747 A CN1030747 A CN 1030747A CN 87104737 CN87104737 CN 87104737 CN 87104737 A CN87104737 A CN 87104737A CN 1030747 A CN1030747 A CN 1030747A
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- nitric acid
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 235000013379 molasses Nutrition 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 19
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 title abstract description 6
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 40
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 23
- 230000003647 oxidation Effects 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000002203 pretreatment Methods 0.000 claims abstract description 10
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 4
- 239000002699 waste material Substances 0.000 claims description 23
- 238000010521 absorption reaction Methods 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 11
- 235000017550 sodium carbonate Nutrition 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 2
- 230000008030 elimination Effects 0.000 claims 2
- 238000003379 elimination reaction Methods 0.000 claims 2
- 206010013786 Dry skin Diseases 0.000 claims 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims 1
- 238000005352 clarification Methods 0.000 claims 1
- XEEVLJKYYUVTRC-UHFFFAOYSA-N oxomalonic acid Chemical compound OC(=O)C(=O)C(O)=O XEEVLJKYYUVTRC-UHFFFAOYSA-N 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 239000002912 waste gas Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 229930006000 Sucrose Natural products 0.000 description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000005720 sucrose Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 229940039748 oxalate Drugs 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910004709 CaSi Inorganic materials 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 108010015776 Glucose oxidase Proteins 0.000 description 1
- 239000004366 Glucose oxidase Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000001875 compounds Chemical group 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- OMBRFUXPXNIUCZ-UHFFFAOYSA-N dioxidonitrogen(1+) Chemical compound O=[N+]=O OMBRFUXPXNIUCZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- -1 enamel Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229940116332 glucose oxidase Drugs 0.000 description 1
- 235000019420 glucose oxidase Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 230000012666 negative regulation of transcription by glucose Effects 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940001516 sodium nitrate Drugs 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Cane molasses is produced the industrial ethanedioic acid method.The invention belongs to the making method of oxalic acid.The present invention adopts the impurity of the pre-treatment of molasses being removed molasses, uses " V in the nitric acid oxidation reaction of molasses
2O
5-Fe
3+-MoO
4 2-" catalyst system and molasses cyclic oxidation, the oxalic acid purifying, thus improved productive rate and purity.Technical process of the present invention is simple, and device fabrication is easy, and energy consumption is low, and environmental pollution is low, the economic benefit height.
Description
The invention belongs to the making method of oxalic acid.
The production method of oxalic acid mainly contains synthetic and oxidation style.W.L.Faith etc. introduce (Industrsal Chemicals Sec.Ed.1957, P553), its synthesis method is raw material with water-gas, first synthesising acid sodium under High Temperature High Pressure, and deoxidation becomes sodium oxalate under high temperature again, acidifying makes oxalic acid, this method has cheap raw material sources, but technical process is long, the condition harshness, its oxidation style is that oxidation forms to carbohydrate (starch) with nitric acid-sulfuric acid, by the productive rate lower (60～70%) of starch nitric acid oxidation.C, A.Bernales etc. introduce (Encgcl, Chem.Technol, 3rd.Ed.1981(16), 618) adopting starch, ethylene glycol, propylene is raw material, under condition of normal pressure, produce oxalic acid by the nitric acid oxidation step, but think that there is the cost height in the nitric acid oxidation method with waste molasses, the how unmanageable problem of foam.
The objective of the invention is to make full use of the agricultural byproducts cane molasses, make it become broad-spectrum industrial ethanedioic acid.Because of in the molasses except that main component sucrose and reducing sugar, also contain a large amount of moisture and non-sugared organism and inorganic ash content, the material composition complexity can be brought out consumption nitric acid.Therefore, adopt pre-treatment to remove impurity and moisture in the molasses in the present invention, and in the nitric acid oxidation reaction of molasses, use composite catalyst, the product yield of its reaction is improved.
The main component of molasses: sucrose and reducing sugar, get oxalic acid through hydrolysis, oxidation, its reaction formula is:
The tail gas nitrogen protoxide that generates absorbs by waste liquor, water and alkali, and recovery can get useful byproducts such as rare nitric acid and nitrate.
Fig. 1 produces the production scheme of industrial ethanedioic acid for of the present invention with cane molasses, and wherein (1) is the molasses header tank; (2) be the nitric acid header tank, the salpeter solution of interior storage 95%; (3) be sulfuric acid high position tank, the sulphuric acid soln of interior storage 45%; (4) be the composite catalyst basin; (5) be the molasses pretreater; (6) be retort; (7) be the gac storage tank; (8) be whizzer; (9) be the waste liquor absorption tower; (10) be the purifying jar; (11) be drying machine; (12) be the product groove; (13) be the water absorption tower; (14) be the soda ash absorption tower.
Now the production scheme in conjunction with Fig. 1 describes as follows to main flow process of production of the present invention and feature.
The pre-treatment of (I) molasses.
Because the material composition complexity of cane molasses, except main component sucrose and reducing sugar (accounting for 50%), also contain have an appointment 40% moisture and other non-sugared organism, inorganic ash content (mainly being CaSi) etc.Impurity in the molasses raw material can bring out and consume nitric acid, and production cost is increased, and makes reaction process produce nonsoluble, and complicated operation, washiness make oxygenant (nitric acid) concentration dilution of reaction process, is unfavorable for that production process improves productive rate.
Thereby adopt pretreated measure in the present invention, promptly the waste liquor of on the one hand molasses being separated through nitric acid oxidation reaction is added in the molasses raw material again molasses raw material is carried out pre-treatment, because of containing the sucrose composition and the nitric acid of some amount in the waste liquor, like this waste liquor being added not only makes effective constituent increase in the molasses raw material, and in preprocessing process, can make molasses water separate certain degree, for the following hydrolysis oxidation stage lays the first stone, improve the efficient of product.Oxalic acid in the mother liquor and calcium salt generation calcium oxalate precipitation can be removed in this operation on the other hand, adds gac simultaneously in preprocessing process, utilizes the adsorption activity of gac to adsorb non-sugared organism and detrimental impurity.Thereby, the nitric acid dosage of reaction is reduced.Carry out press filtration then and concentrate, the moisture in the raw material is reduced to below 10%, to improve concentration of reactants.
(II) hydrolysis and oxidation.
Main component sucrose (C in the molasses
12H
22O
11) under the vitriolic effect hydrolysis become glucose (C
6H
11O
6), glucose generates oxalic acid (H through nitric acid oxidation
2C
2O
4), adopt a step to produce oxalic acid in the present invention.
Because nitric acid not only can make glucose oxidase become oxalic acid, and nitric acid also can further make the oxalic acid oxidation generate carbonic acid gas, and this has not only increased the consumption of nitric acid.And the extraction yield of reduction oxalic acid.In existing oxalic acid oxidation production method, be Primary Catalysts generally, add cocatalysts such as iron, titanium with the vanadium pentoxide.Adopt " V in the present invention
2O
5-Fe
3+-MoO
2- 4" the composite catalyst system, it can make glucose fully be oxidized to oxalic acid through nitric acid, can more effectively suppress the deep oxidation of oxalic acid again.
For the product yield that improves oxalic acid with economize in raw materials, under normal operating condition, adopt Recycling Mother Solution at hydrolysis, oxidation stage, and suitably replenish the catalyzer and the sulfuric acid of necessary amount according to the body series defined terms.The thick product of reacted oxalic acid separates through whizzer, carries out purification process again.
(III) purification process.
The thick product colour of the oxalic acid of separating from whizzer is darker, for improving the purity of oxalate product, the present invention adopts and makes oxalic acid dissolving back add gac, gac decolours to the thick product solution of oxalic acid in the purifying jar, the purified after-filtration of oxalic acid is removed gac and insoluble impurities, heat drying is carried out in crystallization drying machine again, and its crystallization oxalic acid is stored in the product groove, transports for packing.
(IV) off gas treatment.
The nitrous oxides exhaust gas (being mainly nitrogen protoxide) that in the oxidizing reaction of nitric acid, produces to glucose, make waste gas successively by waste liquor absorption tower and water absorption tower and soda ash absorption tower in the present invention, under the air blast situation, make various nitrogen oxides and water effect generate nitric acid.Waste gas becomes the rate of utilization that nitric acid can improve nitric acid through the waste liquor absorption tower; Waste gas enters and becomes rare nitric acid in the water absorption tower then, and tail gas discharged generates SODIUMNITRATE with the yellow soda ash effect on soda ash absorption tower again.Waste gas after handling like this meets the emission standard of country.
Production stage of the present invention is:
A. the pre-treatment of molasses. the waste liquor in molasses stoste in the molasses header tank (1) and waste liquor absorption tower (9), ratio by weight 3～4: 1 is added in the pretreater (5), stirred for several minute under 60 ℃ temperature, be in the gac adding pretreater (5) in 1% gac storage tank (7) by weight after stopping to stir, decolour and clarify a few hours, filter the removal insolubles then, the concentrated solution of going is again reduced to below 10% moisture content.
B. hydrolysis, oxide treatment. start-up function: be molasses, sulfuric acid, composite catalyst in pretreater (5), sulfuric acid high position tank (3), the composite catalyst basin (4) by weight: molasses: catalyzer: sulfuric acid=1000: 1～add in retort (6) at 1.5: 2000.Catalyzer vanadium in the composite catalyst basin, molybdenum, iron are respectively with ammonium vanadate (NH
4V
2O
5), ammonium molybdate ((NH
4)
2MoO
4), ferric sulfate (Fe
2(SO
4)
3) compound form deposit, their ratio is: V: Mo: Fe=2～3: 6～7: 1～3.Make retort (6) be heated to 55 ℃, and raw material stirred, is the nitric acid in the nitric acid header tank (2) slowly to drip advance in retort (6) at 1: 1.6 by the weight ratio of molasses and nitric acid, retort is maintained in 70～75 ℃ of temperature, after adding, nitric acid under 70～75 ℃ of temperature, is incubated 2 hours again, make molasses fully be oxidized to oxalic acid through nitric acid, its waste gas oxynitride enters waste liquor absorption tower (9), handle water absorption tower (13) and soda ash absorption tower (14).Reaction solution is cooled to 6～8 ℃ with frozen water after filtering, makes the oxalic acid crystallization.Then the product in the retort (6) is sent to whizzer (8) and carry out separating of oxalic acid crude product and waste liquor, the thick product of oxalic acid send purifying jar (10) with processing to be purified, waste liquor is input into waste liquor absorption tower (9), uses to make pre-treatment and cyclic oxidation.
Normal running: under normal operational condition, make full use of the effective constituent in the mother liquor, pretreated molasses and waste liquor were added in the retort (6) lentamente by weight 1: 2, and additional composite catalyst and sulfuric acid, make retort (6) be heated to 55 ℃ earlier, slowly add nitric acid again, temperature maintenance is below undertaken by " start-up function " at 70～75 ℃.
C, purification process. the thick product of oxalic acid is sent in the purifying jar (10), adding water and heating (closely boiling) is dissolved as near saturated solution the thick product of oxalic acid, by weight 1% gac is added in the purifying jar (10) again, gac carries out the purifying decolouring to oxalic acid, keep 1 hour time, while hot oxalic acid solution is filtered, remove gac and insolubles impurity, recrystallize.Then the oxalic acid crystallization behind the purifying is changed over to drying machine (11) drying, at last oxalate product is changed over to product groove (12), so that packing is transported.
D, off gas treatment. the nitrogen protoxide waste gas that nitric acid and glucose effect generate in reactor (6), input waste liquor absorption tower (9), it is converted into nitrogen oxides such as nitrogen peroxide under the air blast situation.Waste gas at first with waste liquor in the water effect generate nitric acid, for the usefulness of pre-treatment and cyclic oxidation, its tail gas feeds in the water absorption tower (13) again, generates rare nitric acid with the water effect.Its tail gas feeds soda ash absorption tower (14) again, and the soda ash effect generates nitrate and nitrite, and further processing can obtain nitrate, and the waste gas of Pai Chuing reaches discharging standards at last.
Method of the present invention can be produced 1 ton of oxalic acid with 2 tons of cane molasses, and the sulfuric acid of consumption is 0.9 ton, and nitric acid is 1.6 tons.By national industrial chemicals price in 1980, produce the pure profit that oxalic acid per ton can get and be not less than 500 yuan.
Of the present inventionly produce the method for industrial ethanedioic acid with cane molasses, its technological process is simple, and single step reaction can obtain to meet the product of national HGZ-169-78 standard; Low in the pollution of the environment; Carry out equipment because of technique under condition of normal pressure and only have Anticorrosion, generally can adopt stainless steel, enamel, plastic or other material are made; The key reaction of this technique is exothermic reaction, so energy resource consumption is low; Economic benefit is higher.
Claims (2)
1, a kind of method of making oxalic acid through nitric acid oxidation with molasses is used composite catalyst when it is characterized in that molasses through pre-treatment with at nitric acid oxidation, and making method is:
A, molasses and waste liquor are added the pretreater [5] by weight 3～4: 1 from [1] and [9], stirred for several minute under 60 ℃ of temperature, stop to stir the back and the gac of [7] added by weight 1%, after decolouring clarification a few hours molasses elimination insolubles reconcentration extremely moisture 10%;
B, start-up function: the sulfuric acid of 45% in the molasses in after pre-treatment [5] and [3], [4] composite catalyst in, add in the retort [6] by weight 1000: 2000: 1～1.5, be heated to 55 ℃ and stir, be the nitric acid of 95% in [2] slowly to splash in retort [6] at 1.6: 1 by it and molasses weight ratio again, maintain in 70～75 ℃ of temperature, after adding, nitric acid is incubated 2 hours at 70～75 ℃ again, reaction solution is cooled to 6～8 ℃, make the oxalic acid crystallization, through whizzer [8] the oxalic acid coarse crystallization is separated with waste liquor, the oxalic acid coarse crystallization is sent purifying jar [10], and waste liquor changes over to and gives over to pre-treatment and cyclic oxidation use in the waste liquor absorption tower [9];
Normal running: with the molasses of pretreated [5] and the waste liquor of [9] be by weight: slowly add in retort [6] at 1: 2, and additional composite catalyst and sulfuric acid, be heated to 55 ℃ and stir, slowly add nitric acid again, make molasses be oxidized to oxalic acid (following operation is with " start-up function ");
C, the thick product of purifying jar [10] mesoxalic acid is dissolved in water and heats closely boil, from [7], add gac by weight 1%, the purifying 1 hour of decolouring, elimination insolubles recrystallize while hot, entering drying machine [11] then becomes the oxalic acid crystalline product in 100 ℃ of dryings;
The nitrogen protoxide that d, nitric acid and glucose response generate is separately converted to nitrate or nitrite through waste liquor absorption tower [9], water absorption tower [13] and soda ash absorption tower [14] under the air blast condition.
2, method according to claim 1 is characterized in that composite catalyst is " V
2O
5-Fe
3+-MoO
2- 4" system, it is than being: V: Mo: Fe=2～3: 6～7: 1～3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87104737 CN1030747A (en) | 1987-07-07 | 1987-07-07 | Cane molasses is produced the industrial ethanedioic acid method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87104737 CN1030747A (en) | 1987-07-07 | 1987-07-07 | Cane molasses is produced the industrial ethanedioic acid method |
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| Publication Number | Publication Date |
|---|---|
| CN1030747A true CN1030747A (en) | 1989-02-01 |
Family
ID=4814991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87104737 Pending CN1030747A (en) | 1987-07-07 | 1987-07-07 | Cane molasses is produced the industrial ethanedioic acid method |
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| Country | Link |
|---|---|
| CN (1) | CN1030747A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664575A (en) * | 2013-12-12 | 2014-03-26 | 应县锦华科技实业有限责任公司 | Method for producing oxalic acid |
-
1987
- 1987-07-07 CN CN 87104737 patent/CN1030747A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664575A (en) * | 2013-12-12 | 2014-03-26 | 应县锦华科技实业有限责任公司 | Method for producing oxalic acid |
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