CN100560557C - The method for preparing formic acid with acidifying sodium formate with acidification adjuvant - Google Patents
The method for preparing formic acid with acidifying sodium formate with acidification adjuvant Download PDFInfo
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- CN100560557C CN100560557C CNB2007100498375A CN200710049837A CN100560557C CN 100560557 C CN100560557 C CN 100560557C CN B2007100498375 A CNB2007100498375 A CN B2007100498375A CN 200710049837 A CN200710049837 A CN 200710049837A CN 100560557 C CN100560557 C CN 100560557C
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- formic acid
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- inhibitor
- ether
- sodium formate
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 102
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 51
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000020477 pH reduction Effects 0.000 title claims abstract description 13
- 239000004280 Sodium formate Substances 0.000 title claims abstract description 8
- 239000002671 adjuvant Substances 0.000 title claims abstract description 8
- 235000019254 sodium formate Nutrition 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000003112 inhibitor Substances 0.000 claims abstract description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 14
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical group CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 11
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 6
- RMOUBSOVHSONPZ-UHFFFAOYSA-N Isopropyl formate Chemical compound CC(C)OC=O RMOUBSOVHSONPZ-UHFFFAOYSA-N 0.000 claims description 4
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- ZDPALFHDPFYJDY-UHFFFAOYSA-N [Na].OC=O Chemical compound [Na].OC=O ZDPALFHDPFYJDY-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 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
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- AVMSWPWPYJVYKY-UHFFFAOYSA-N 2-Methylpropyl formate Chemical compound CC(C)COC=O AVMSWPWPYJVYKY-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method that adopts acidifying sodium formate with acidification adjuvant to prepare formic acid, it is to add inhibitor in reaction process, described inhibitor is that boiling point is lower than at least a in 80 ℃ alkane, naphthenic hydrocarbon, ether or the manthanoate, the present invention is control reaction temperature effectively, suppresses the generation of side reaction, and the acquisition recovery rate is 98% formic acid, the concentration that can prepare is 98% concentration formic acid and high, and easy to operate, safety economy, pollution effectively can control environment.
Description
Technical field
The present invention relates to a kind of preparation method of formic acid, specifically adopt acidifying sodium formate with acidification adjuvant to prepare the method for formic acid.
Background technology
Be known that, prepare formic acid by sodium formiate, can add sulfuric acid, phosphoric acid, peroxophosphoric acid or acidification adjuvant acidifyings such as polymer phosphate, Vanadium Pentoxide in FLAKES and prepare formic acid, Chinese patent 97103209.2,200610124470.4,200610200857.3 discloses the method that various acidifying sodium formate with acidification adjuvant prepare formic acid, and it is effective that these methods were checked by production practice.But because acidifying is thermopositive reaction, and formic acid decomposes under local superheating easily, produces carbon monoxide and water; If decomposition temperature is greater than 100 ℃, formic acid is understood oxidized generation carbonic acid gas and water, and the water of generation causes the concentration of formic acid not high, can not obtain the concentration formic acid and high more than 95%; Further also can produce yellow soda ash, not only can reduce the concentration of formic acid greatly, can bring more that by product is many, the formic acid quality descends and the problem of serious three wastes.
Chinese patent 200610200857.3 discloses a kind of method of preparation 95% concentration formic acid and high, it is that to contain reductibility polycomponent polymer phosphate mixture by employing be that souring agent comes acidifying sodium formate to produce the formic acid of 95% high density, its principle is to utilize the interior moisture of high absorption property absorption reaction system of polymer phosphate mixture, thereby improve the concentration of formic acid, but, the shortcoming of this technology is that the usage quantity of polymer phosphate mixture will increase, also may adsorb a certain amount of formic acid, though it claims to obtain the formic acid of 95% high density, but in the production process of reality, be not reach this concentration far away, in addition, its subsequent treatment process is with respect to conventional art, and is complicated more.
Summary of the invention
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art and a kind of method for preparing concentration formic acid and high is provided, this method can control reaction temperature, the generation of restriction side reaction, and easy and simple to handle.
The object of the present invention is achieved like this:
Considering needs control reaction temperature below 80 ℃ in the sodium formiate acidization, if a large amount of heats in the reaction process can be taken away equably, can realize, for this reason, the present invention is based on the following aspects and consider, add the temperature of one or more inhibitor control reactions:
The one, any material in this inhibitor discord reaction system reacts;
The 2nd, the boiling point of this inhibitor is lower than 80 ℃;
The 3rd, this inhibitor is nontoxic, to product quality without any influence.
For this reason, technical scheme of the present invention is to add inhibitor in the reaction process for preparing formic acid with acidifying sodium formate with acidification adjuvant, and described inhibitor is that boiling point is lower than at least a in 80 ℃ alkane, naphthenic hydrocarbon, ether or the manthanoate.
Wherein, the add-on of described inhibitor preferably is not less than 5% of sodium formiate weight, and by repeatedly experiment discovery, add-on is less than at 5% o'clock, and formic acid decomposes easily, and reaction is not easy control; And be higher than 10%, and the inhibitor evaporation time that not only extended also causes the loss of inhibitor easily, and therefore, best scheme is that the add-on of inhibitor is the 5-10% of sodium formiate weight.
Described alkane comprises that pentane, hexane or boiling point are lower than 80 ℃ of solvent oils;
Described naphthenic hydrocarbon comprises hexanaphthene, pentamethylene or cyclopropane;
Described ether comprises isopropyl ether, ether or propyl ether;
Described manthanoate comprises isopropyl formate, propyl formate or tetryl formate.
The present invention has following advantage than prior art:
Because the present invention in the acidification reaction system, selected not with reaction system in any substance reaction, nontoxic and boiling point at the inhibitor that is lower than 80 ℃, in case reaction system is overheated, the volatilization of promptly absorbing heat of these lower boiling inhibitor, take away a large amount of acidification reaction liberated heats, thereby controlled the temperature of reaction system effectively, avoid local temperature too high and cause formic acid to decompose, avoided the generation of side reactions such as hydrolysis, oxidation, can make the formic acid recovery rate greater than 98%, make formic acid content greater than 98% concentration formic acid and high; In addition,, make acidification reaction carry out under the normal temperature and pressure again, need not add any utility appliance just because of having selected this inhibitor, easy to operate; Nontoxic inhibitor, for the quality that guarantees product, the Optimizing operation environment, control is polluted also clearly effect.In addition, the inhibitor after the volatilization can also be used in the Returning reactor again after condensation, both saved resource, reduced production cost again.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, but protection scope of the present invention has more than and is limited to these examples:
Embodiment 1: in reactor, add anhydrous formic acid sodium, add boiling range 40-60 ℃ pentane of sodium formiate charging capacity 6%, be metered into 98% sulfuric acid, reaction heat is taken reactor out of by gasifying pentane, through 10-20 ℃ of cooling water temperature, and Returning reactor again after the condensation.When 98% the sulfuric acid rate of addition control of metering 1-2 hour, add the back and continue reaction 20-30 minute, do not heat up in a steamer up to having back, steam solvent under 80 ℃, the later stage rough vacuum steams to formic acid to go out to heat up in a steamer, the pentane of recovery and a small amount of formic acid, be used for next batch sodium formiate acidification reaction, solvent recovering rate is greater than 96%.The reaction mass that has taken off solvent steams formic acid under the 0.03-0.04MPa absolute pressure, formic acid content is greater than 94%, and recovery rate is greater than 98%.
Embodiment 2: in reactor, add anhydrous formic acid sodium, the pentamethylene that adds sodium formiate charging capacity 6%, be metered into 100% phosphoric acid (available 85% phosphoric acid and 105% peroxophosphoric acid mixed preparing) 60 ± 5 ℃ of reactions, reaction heat is taken reactor out of by the pentamethylene vaporization, by 10-20 ℃ of cooling water temperature, Returning reactor again after the condensation, 100% phosphoric acid rate of addition control 1-2 hour adds the back and continues reaction 20-30 minute, does not uprightly have back and heats up in a steamer, under 80 ℃, steam solvent, later stage rough vacuum to formic acid goes out to heat up in a steamer, and reclaims pentamethylene and a small amount of formic acid, is used for next batch sodium formiate acidification reaction, solvent recovering rate is greater than 96%, the reaction mass that has taken off solvent steams formic acid under the 0.03-0.04MPa absolute pressure, formic acid content is greater than 96%, and recovery rate is greater than 98%.
Embodiment 3: in reactor, add anhydrous formic acid sodium, add sodium formiate charging capacity 8% isopropyl ether, be metered into 100% phosphoric acid, in reaction below 80 ℃, reaction heat is taken reactor out of by the isopropyl ether vaporization, by 20 ℃ of cooling water temperatures, Returning reactor again after the condensation, 100% phosphoric acid rate of addition control 1-2 hour, add the back and continue reaction 20-30 minute, uprightly do not have back and heat up in a steamer, steaming isopropyl ether below 80 ℃, the later stage steams a small amount of isopropyl ether under the 50MPa absolute pressure, go out to heat up in a steamer until formic acid, reclaim isopropyl ether and be used for secondary response down, solvent recovering rate is greater than 96%, and the reaction mass that has taken off behind the solvent steams formic acid under the 0.03-0.04MPa absolute pressure, formic acid content is greater than 96%, and recovery rate is greater than 98%.
Embodiment 4: the technology of pressing embodiment 1, the sodium formiate charging capacity isopropyl formate of adding 8%, the peroxophosphoric acid of dropping 102%, the reaction control reaction temperature is less than 80 ℃ under the 40-50MPa absolute pressure, peroxophosphoric acid rate of addition 1-2 hour, adopt the same quadrat method of previous examples, under 80 ℃, steam isopropyl formate, go out to heat up in a steamer until formic acid, solvent recovering rate is greater than 95%, formic acid steams formic acid after having taken off solvent under the 0.03-0.04MPa absolute pressure, and the formic acid yield is greater than 98%, and formic acid content is greater than 98%.
Embodiment 5: in reactor, add anhydrous formic acid sodium, drip stoichiometry isopropyl ether and concentration phosphoric acid by wet process extraction liquid, wherein phosphorus acid content 42%, reaction heat is steamed by isopropyl ether and takes away, with reclaiming after 20 ℃ of water quench, control reaction temperature dripped time 1-2 hour less than 80 ℃, adopt above-mentioned example to reclaim isopropyl ether and formic acid, formic acid content is greater than 98%, and the formic acid yield is greater than 98%, and SODIUM PHOSPHATE, MONOBASIC can reach the food grade standard.
Embodiment 6: in reactor, add anhydrous formic acid sodium, the isopropyl ether of the sodium formiate charging capacity of adding 8% mixes with the mixed solvent of pentamethylene, volume ratio 1: 1, drip 100% phosphoric acid, dripping 100% phosphoric acid, rate of addition 1-2 hour below 80 ℃, adopt the same quadrat method of previous examples, steam mixed solvent under 80 ℃, solvent recovering rate is greater than 96%, steams formic acid after having taken off solvent under 0.03-0.04MPa, the formic acid yield is greater than 98%, and formic acid content is greater than 96%.
Claims (5)
1, the method for preparing formic acid with acidifying sodium formate with acidification adjuvant, it is characterized in that in reaction process, adding inhibitor, described inhibitor is that at least a and boiling point in alkane, naphthenic hydrocarbon, ether or the manthanoate is lower than 80 ℃, and the add-on of described inhibitor is the 5-10% of sodium formiate weight.
2, method according to claim 1 is characterized in that described alkane is that pentane, hexane or boiling point are lower than 80 ℃ of solvent oils.
3, method according to claim 1 and 2 is characterized in that described naphthenic hydrocarbon is pentamethylene or cyclopropane.
4, method according to claim 1 and 2 is characterized in that described ether is isopropyl ether or ether.
5, method according to claim 1 and 2 is characterized in that described manthanoate is an isopropyl formate.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100498375A CN100560557C (en) | 2007-08-24 | 2007-08-24 | The method for preparing formic acid with acidifying sodium formate with acidification adjuvant |
| PCT/CN2007/071086 WO2009026773A1 (en) | 2007-08-24 | 2007-11-17 | Process for producing formic acid by acidifying sodium formate with acidifying agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100498375A CN100560557C (en) | 2007-08-24 | 2007-08-24 | The method for preparing formic acid with acidifying sodium formate with acidification adjuvant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101139279A CN101139279A (en) | 2008-03-12 |
| CN100560557C true CN100560557C (en) | 2009-11-18 |
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| CNB2007100498375A Active CN100560557C (en) | 2007-08-24 | 2007-08-24 | The method for preparing formic acid with acidifying sodium formate with acidification adjuvant |
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| CN (1) | CN100560557C (en) |
| WO (1) | WO2009026773A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180036635A (en) * | 2016-09-30 | 2018-04-09 | 한국화학연구원 | Method of recovering highly concentrated formic acid and highly concentrated sulfate from formate aqueous solution, and recovery apparatus |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106800505A (en) * | 2015-11-25 | 2017-06-06 | 衡阳屹顺化工有限公司 | A kind of method for preparing concentration formic acid and high |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3114312A1 (en) * | 1981-04-09 | 1982-10-21 | Davy McKee AG, 6000 Frankfurt | Process for the preparation of formic acid |
| CN1153767A (en) * | 1995-12-09 | 1997-07-09 | 陈广生 | Formic acid and sodium sulfate producing method |
| CN1821205A (en) * | 2006-03-21 | 2006-08-23 | 尚微 | Process for producing formic acid |
| CN1915823A (en) * | 2006-08-23 | 2007-02-21 | 湖北宜化集团有限责任公司 | Method for preparing sodium sulfate in high purity |
| CN1915954A (en) * | 2006-09-07 | 2007-02-21 | 湖北兴发化工集团股份有限公司 | Method for producing formic acid through phosphoric acid and sodium formate |
| CN1994999A (en) * | 2006-09-11 | 2007-07-11 | 左建国 | 95% high concentration formic acid production method |
-
2007
- 2007-08-24 CN CNB2007100498375A patent/CN100560557C/en active Active
- 2007-11-17 WO PCT/CN2007/071086 patent/WO2009026773A1/en active Application Filing
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180036635A (en) * | 2016-09-30 | 2018-04-09 | 한국화학연구원 | Method of recovering highly concentrated formic acid and highly concentrated sulfate from formate aqueous solution, and recovery apparatus |
| KR101985444B1 (en) | 2016-09-30 | 2019-06-03 | 한국화학연구원 | Method of recovering highly concentrated formic acid and highly concentrated sulfate from formate aqueous solution, and recovery apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009026773A1 (en) | 2009-03-05 |
| CN101139279A (en) | 2008-03-12 |
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Application publication date: 20080312 Assignee: YIBIN HAIFENG HERUI Co.,Ltd. Assignor: YIBIN TIANYUAN GROUP Co.,Ltd. Contract record no.: X2022980029850 Denomination of invention: Preparation of formic acid by acidification of sodium formate with acidification assistant Granted publication date: 20091118 License type: Common License Record date: 20221230 |
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