CN101665423B - Method for preparing methanoic acid by potassium formate acidized by phosphoric acid - Google Patents
Method for preparing methanoic acid by potassium formate acidized by phosphoric acid Download PDFInfo
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- CN101665423B CN101665423B CN2009100603192A CN200910060319A CN101665423B CN 101665423 B CN101665423 B CN 101665423B CN 2009100603192 A CN2009100603192 A CN 2009100603192A CN 200910060319 A CN200910060319 A CN 200910060319A CN 101665423 B CN101665423 B CN 101665423B
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- potassium
- formic acid
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- phosphoric acid
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- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 83
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 38
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims abstract description 28
- 239000006227 byproduct Substances 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 76
- 230000020477 pH reduction Effects 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 5
- 230000002459 sustained effect Effects 0.000 claims description 5
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract description 3
- 238000007599 discharging Methods 0.000 abstract 1
- 229910000160 potassium phosphate Inorganic materials 0.000 abstract 1
- 235000011009 potassium phosphates Nutrition 0.000 abstract 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 13
- 239000000203 mixture Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000004280 Sodium formate Substances 0.000 description 5
- 235000019254 sodium formate Nutrition 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000010025 steaming Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 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
- 238000000605 extraction Methods 0.000 description 2
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
Abstract
The invention discloses a method for preparing methanoic acid by reaction of potassium formate and phosphoric acid, which comprises the following steps: firstly, adding the potassium formate and the phosphoric acid into a reaction container for acidizing reaction to prepare methanoic acid gas; secondly, evaporating the methanoic acid and purifying the methanoic acid, obtaining the high-concentration methanoic acid product after cooling; discharging side products, regulating P/K value of the side products, i.e. preparing various kinds of potassium phosphate. The invention has high continuity degree, low energy consumption and convenient operation, greatly lowers the cost, improves the economic benefit and can prepare the high-concentration methanoic acid.
Description
Technical field
The present invention relates to the preparation method of a kind of formic acid and an alkali metal salt, specifically adopt the method for phosphoric acid and potassium formiate prepared in reaction formic acid.
Background technology
Be known that; Prepare formic acid by sodium formiate, can add sulfuric acid, phosphoric acid, peroxophosphoric acid or acidifying sodium formate with acidification adjuvant 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; It is effective that these methods were checked by production practice; Wherein, prepare formic acid by the sulfuric acid acidation sodium formiate, the sodium sulfate use value that obtains after the acidifying is lower; And discharge also serious environment pollution of a large amount of carbonic acid gas, this method is eliminated basically; And with the method for phosphoric acid, polyphosphoric acid acidifying sodium formiate system formic acid; Because but the SODIUM PHOSPHATE, MONOBASIC that its coproduction has certain use value is further produced other phosphoric acid salt, like tripoly phosphate sodium STPP and Sodium hexametaphosphate 99; Therefore and pollute lessly, in industry, be able to generally adopt.But, prepare the technology of formic acid with the phosphoric acid acidifying sodium formate, there is following shortcoming:
One, reaction is not exclusively: because sodium formiate is a solid matter, with the reaction of phosphoric acid be solid-liquid reaction, even if under agitation condition; Therefore the denseness of system is still very high, mixes still inhomogeneously, needs to increase stirring intensity; Not only increase energy consumption, and caused reaction not exclusively; In addition, because acidification reaction is thermopositive reaction, formic acid is overflowed, and has further increased the denseness of system, has increased the weight of the incomplete degree of reaction; Moreover; After acidification reaction takes place; The SODIUM PHOSPHATE, MONOBASIC that generates is coated on the outside of solid sodium formate, shielded contacting of sodium formiate and phosphoric acid, increased the weight of the incomplete degree of acidification reaction once more; Cause the waste of a large amount of sodium formiate raw materials, also have certain influence for the quality of the various sodium phosphate salts of subsequent preparation.
Two, reaction is discontinuous: owing to be solid-liquid reaction, therefore must guarantee system in certain quantity of solvent, otherwise will make the denseness of system increase or become solid-state completely, can not normal reaction, and the formic acid in the system be product also is primary solvent.Conventional; After in reactor drum, adding sodium formiate and phosphoric acid; To produce certain acidification reaction in the preliminary mixing process, and at this moment can not the formic acid that produce be extracted out at once, because must keep a certain amount of formic acid as solvent; Guarantee the solid-liquid ratio in the reaction system, this just makes whole technology discontinuous;
Three, it is not high to obtain the concentration of formic acid, and subsequent treatment process is complicated: in the acidification reaction process, the prerequisite of the formic acid gas of its extraction also be must guarantee system in as the amount of formic acid of solvent; This will cause a following new difficult problem to occur: because acidifying is thermopositive reaction; And formic acid decomposes under local superheating easily, produces carbon monoxide and water, and the water of generation causes the concentration of formic acid not high; Cleaning section for follow-up is had higher requirement; Such as how removing carbon monoxide, the water-containing formic acid of this dilution can not be recovered as the formic acid of high density easily through distillation, can not obtain the concentration formic acid and high product after causing condensation; 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.
Therefore, existingly prepare the technology of formic acid with the phosphoric acid acidifying sodium formate and since its exist reaction not exclusively, technology serialization degree is not high, energy consumption is high, the not high problem of formic acid quality of preparation makes it can not be applicable to that industrial scale uses.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art and a kind of phosphoric acid and potassium formiate of adopting is provided is the method for the high-quality formic acid of raw material production, and not only serialization degree of this method is high, energy consumption is low, but also has characteristics easy and simple to handle.
The objective of the invention is to realize like this:
A kind ofly prepare the method for formic acid, comprise the steps: with phosphoric acid and potassium formiate
(1) initial reaction: phosphoric acid and potassium formiate joined by the amounts of reactants of phosphoric acid and potassium formiate mix in the reactor drum and carry out initial reaction, obtain the mixture of formic acid and potassium phosphate salt, utilize reaction heat to guarantee the temperature of reaction system rising.Because the reaction of phosphoric acid and potassium formiate is thermopositive reaction, the part acidified reaction can take place in mixed phosphate and sodium formiate, produces formic acid, and discharges a large amount of heats, makes temperature of reaction system increase rapidly, causes solid-state potassium formiate dissolving.
(2) acidification reaction: temperature of reaction system rises to the potassium formiate dissolving, makes liquid potassium formiate and phosphoric acid sustained reaction obtain the mixture of formic acid and potassium phosphate salt; In continuous acidification reaction process, it is liquid that the heat that reaction is discharged can keep reaction system basically, if temperature is not enough in the system, it is liquid can also coming guarantee system through type of heating.
(3) distillation: under condition of negative pressure, go out the formic acid in (1), (2) step, again formic acid is purified, obtains the formic acid product after the condensation process through the distillation consecutive evaporation.Condition of negative pressure is confirmed according to the formic acid gas vol that is produced, on the whole; Assurance formic acid gas is extracted out rapidly is advisable, and is preferably, and the weight content that guarantees the formic acid that reaction system is interior is the 1.0-2% of material gross weight in the system; Be higher than 2% and can quicken to extract out, be lower than 1.0% extraction of can slowing down; For purification, the condensation process of water-containing formic acid, identical with usual manner.
Wherein, the phosphoric acid of the present invention's use is with P
2O
5Content (weight) meter reaches the phosphoric acid of 70-80%; The purity of the potassium formiate that uses is 95-99.99%, and said purity is the massfraction of potassium formiate; Described P/K value is P
2O
5And K
2The mol ratio of O.
In order to obtain better economical effectiveness, can be when producing formic acid, the preparation potassium phosphate salt, after the by product that promptly steams formic acid was discharged reactor drum, the P/K value of regulating this by product made various potassium phosphate salts.
Wherein, described potassium phosphate salt is various compound phosphoric acid sylvite such as potassium primary phosphate, potassium hydrogenphosphate, Tripotassium phosphate, hexa metaphosphoric acid potassium, Potassium tripolyphosphate.
The present invention has following advantage than prior art:
Because the present invention successfully with phosphoric acid and potassium formiate as the raw material of producing formic acid; Utilize potassium formiate in 165 ℃ of dissolvings, solubleness is big, water binding is strong character; Original solid-liquid reaction is changed into liquid-liquid reactions, make that reaction is more complete, more abundant to the use of raw material; Simultaneously, make full use of the heat of this thermopositive reaction of acidification reaction, not only made reaction system reach the requirement of dissolving potassium formiate, also reduced energy consumption effectively; In addition, in order to solve the resolution problem of formic acid, adopt negative pressure to begin promptly to carry out round-the-clock the distillation from initial reaction; Make that the survival time of formic acid in reactor drum is shorter, the decomposition reaction odds is littler, has guaranteed to steam the purity and the concentration of formic acid effectively; Can make the formic acid yield greater than 97%; Make formic acid content greater than 97% concentration formic acid and high, fundamentally guaranteed the quality of formic acid product, can access the high formic acid product of purity and concentration; Moreover, the various potassium phosphate salts of coproduction when producing formic acid, owing to the price of potassium phosphate salt with respect to sodium phosphate salt exceeds a lot, therefore the economy of whole technology is better, has reduced the production cost of formic acid indirectly; Simultaneously,, need not carry out the mensuration or the adjustment of pH value, only need calculate and adjust, can realize the preparation of different phosphate acid potassium salt, simplify production technique the P/K value for the various potassium phosphate salts of by-product.
Embodiment
Below in conjunction with embodiment the present invention is done to specify further, but protection scope of the present invention has more than and is limited to these examples:
Embodiment 1:
(1) initial reaction: will be with (P
2O
5Weight content meter 70%) to be 95% potassium formiate by the amounts of reactants of phosphoric acid and potassium formiate join carries out the mixture that initial reaction obtains formic acid and potassium phosphate salt in the reactor drum for phosphoric acid and purity (mass percent), through reaction heat the temperature of reaction system risen;
(2) acidification reaction: temperature of reaction system rises to the potassium formiate dissolving, makes liquid potassium formiate and phosphoric acid sustained reaction obtain the mixture of formic acid and potassium phosphate salt;
(3) distillation: under the 0.03-0.04MPa absolute pressure, go out the formic acid in (1), (2) step through the distillation consecutive evaporation, again formic acid gas being purified, obtain after the condensation process concentration is 97% formic acid;
(4) preparation potassium phosphate salt: after steaming the by product discharge reactor drum of formic acid, regulate the K of this by product
2O/P
2O
5Mol ratio be 1.0 ± 0.003, make potassium primary phosphate.
Embodiment 2:
(1) initial reaction: will be with (P
2O
5Weight content meter 80%) to be 99.99% potassium formiate by the amounts of reactants of phosphoric acid and potassium formiate join carries out the mixture that initial reaction obtains formic acid and potassium phosphate salt in the reactor drum for phosphoric acid and purity (mass percent), through reaction heat the temperature of reaction system risen;
(2) acidification reaction: temperature of reaction system rises to the potassium formiate dissolving, makes liquid potassium formiate and phosphoric acid sustained reaction obtain the mixture of formic acid and potassium phosphate salt;
(3) distillation: under the 0.03-0.04MPa absolute pressure, go out the formic acid in (1), (2) step through the distillation consecutive evaporation, again formic acid gas being purified, obtain after the condensation process concentration is 98% formic acid;
(4) preparation potassium phosphate salt: after steaming the by product discharge reactor drum of formic acid, regulate the K that makes of this by product
2O/P
2O
5Mol ratio be 1.667 ± 0.003, send in the polymerization furnace, through polymerization, cooling, pulverizing, packing and the Potassium tripolyphosphate finished product.
Embodiment 3:
(1) initial reaction: will be with (P
2O
5Weight content meter 76.5%) to be 97% potassium formiate by the amounts of reactants of phosphoric acid and potassium formiate join carries out the mixture that initial reaction obtains formic acid and potassium phosphate salt in the reactor drum for phosphoric acid and purity (mass percent), through reaction heat the temperature of reaction system risen;
(2) acidification reaction: temperature of reaction system rises to the potassium formiate dissolving, makes liquid potassium formiate and phosphoric acid sustained reaction obtain the mixture of formic acid and potassium phosphate salt;
(3) distillation: under the 0.03-0.04MPa absolute pressure, go out the formic acid in (1), (2) step through the distillation consecutive evaporation, again formic acid gas being purified, obtain after the condensation process concentration is 97% formic acid;
(4) preparation potassium phosphate salt: after steaming the by product discharge reactor drum of formic acid, regulate the K of this by product
2O/P
2O
5Mol ratio be 1.0 ± 0.003, send in the polymerization furnace, through polymerization, cooling, pulverizing, packing and hexa metaphosphoric acid potassium finished product.
Claims (6)
1. one kind with the potassium formate acidized method for preparing formic acid of phosphoric acid, it is characterized in that comprising the steps:
(1) initial reaction: phosphoric acid and potassium formiate joined by the amounts of reactants of phosphoric acid and potassium formiate mix in the reactor drum and carry out initial reaction, obtain formic acid and potassium phosphate salt, utilize reaction heat to guarantee that temperature of reaction system rises;
(2) acidification reaction: temperature of reaction system rises to the potassium formiate dissolving, makes liquid potassium formiate and phosphoric acid sustained reaction obtain formic acid and potassium phosphate salt;
(3) distillation: under condition of negative pressure, go out the formic acid in (1), (2) step, again formic acid is purified, obtains the formic acid product after the condensation process through the distillation consecutive evaporation.
2. method according to claim 1 is characterized in that at described phosphoric acid be with P
2O
5The content meter reaches the phosphoric acid of 70-80%.
3. method according to claim 1, the purity that it is characterized in that described potassium formiate is 95-99.99%.
4. according to claim 1,2 or 3 described methods, it is characterized in that in (3) distilation steps that the weight content of the formic acid in the reaction system is the 1.0-2% of material gross weight in the system.
5. method according to claim 1 is characterized in that also comprising the step for preparing potassium phosphate salt, promptly steams after the by product of staying behind the formic acid in the reaction system discharges reactor drum, and the P/K value of regulating this by product makes various potassium phosphate salts.
6. method according to claim 5 is characterized in that described potassium phosphate salt is potassium primary phosphate, potassium hydrogenphosphate, Tripotassium phosphate, hexa metaphosphoric acid potassium, the various compound phosphoric acid sylvite of Potassium tripolyphosphate.
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| CN101665423B true CN101665423B (en) | 2012-11-21 |
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| CN105084335B (en) * | 2014-05-12 | 2017-04-12 | 天津市碳一有机合成工程设计有限公司 | Cogeneration method for producing monopotassium phosphate and potassium diformate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1179413A (en) * | 1997-03-18 | 1998-04-22 | 贵州磷酸盐厂 | Method for producing formic acid and coproducing various sodium phosphate salts by acidifying sodium formate with perphosphoric acid |
| 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 |
| CN101139278A (en) * | 2007-08-24 | 2008-03-12 | 宜宾天原集团股份有限公司 | Method for preparing formic acid by extraction of phosphorus acid and sodium formate |
-
2009
- 2009-08-11 CN CN2009100603192A patent/CN101665423B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1179413A (en) * | 1997-03-18 | 1998-04-22 | 贵州磷酸盐厂 | Method for producing formic acid and coproducing various sodium phosphate salts by acidifying sodium formate with perphosphoric acid |
| 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 |
| CN101139278A (en) * | 2007-08-24 | 2008-03-12 | 宜宾天原集团股份有限公司 | Method for preparing formic acid by extraction of phosphorus acid and sodium formate |
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