CN103601630A - Method utilizing calcium carbide slag and carbon monoxide to synthesize calcium formate - Google Patents
Method utilizing calcium carbide slag and carbon monoxide to synthesize calcium formate Download PDFInfo
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- CN103601630A CN103601630A CN201310281962.4A CN201310281962A CN103601630A CN 103601630 A CN103601630 A CN 103601630A CN 201310281962 A CN201310281962 A CN 201310281962A CN 103601630 A CN103601630 A CN 103601630A
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
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Abstract
The invention relates to a method utilizing calcium carbide slag and carbon monoxide to synthesize calcium formate. The method is characterized in that: the method utilizes calcium carbide slag generated during the process of acetylene production using a calcium carbide method and carbon monoxide obtained from yellow phosphorus tail gas, calcium carbide furnace tail gas, or other sources to synthesize calcium formate, and comprises the following steps: first subjecting calcium carbide slag to a pretreatment, then converting the slag into slurry, filtering and sieving the slurry, grinding, then mixing with purified carbon monoxide obtained from yellow phosphorus tail gas, calcium carbide furnace tail gas, or other sources, and transporting the mixture to a reactor to carry out counter-current reactions so as to obtain calcium formate. This method comprehensively utilizes waste water, waste gas, waste solid, and by-products generated during the industrial production, also produces a food-grade calcium formate product, and has the advantages of short reaction time, low cost, little environmental pollution, and high comprehensive economic profit.
Description
Technical field
The present invention relates to a kind of method of utilizing carbide slag and the synthetic calcium formiate of carbon monoxide.
Background technology
Calcium formiate is a kind of broad-spectrum fodder additives, is applicable to various animal-feeds, can be used as souring agent, sanitas and antiseptic-germicide.German Research finds, adds the generation that 0.9% calcium formiate can reduce diarrhoea in piglet grain ration, adds 1.3% and can improve feed conversion rate 7.8%, adds 1.5% and can improve piglet productivity 1.2%, feed conversion rate 4%; Domestic research shows to add 1%～1.5% calcium formiate in 8 week of piglet grain ration, can prevent that diarrhoea and diarrhea from occurring, and raising surviving rate, improves food conversion ratio 7%～10%; Feed intake declines 3.8%, and daily gain in pigs 9%～13% adds calcium formiate and can improve lactic acid content in silage, reduces butyric acid content, increases the nutritive ingredient of silage.
The evidence of Gansu Province research of agricultural science institute, the plant growth regulator treatment farm crop that are main component with calcium formiate, can promote chlorophyll to increase, regulate photosynthesis, intensify the activity of enzyme, promote crop to germinate, accelerating growth, stimulate ovary increasing, reduce ghost rate, increase dry granular weight, reduce fallen flowers, shedding, can make increasing crop yield 10% left and right such as wheat, corn, melon and fruit, vegetables, to person poultry harmless, easy to use.
High purity calcium formiate can be made oral liquid, is used for the treatment of the calcium deficiency of human body, the medicine of replenishing the calcium on the market, large multiplex it make.
In construction industry, calcium formiate is for cement rapid solidification agent, lubricant and hardening accelerator.Calcium formiate adds in cement, can accelerate the setting time of cement, shortens time of coagulation.Calcium formiate can significantly improve quality and the characteristic of ceramic tile adhesive, can extend working time and improve tack.
Calcium formiate can also be made sweetening agent, process hides auxiliary agent of high-sulfur combustion product gases etc.
Formic acid mainly adopts following method to produce:
1, the use water-ground limestone such as the Zhao Wei of Zhejiang University honor and calcium hydroxide reclaim the formic acid that reaction adds from epoxy soybean oil waste water, prepare calcium formiate (CN1793103/A), and the calcium formiate quality of recovery is as follows:
2, Zhao Yongjie etc. has invented from tetramethylolmethane is synthetic, with formic acid precipitated calcium ion, obtains calcium formiate (CN1762963/A) preparing tetramethylolmethane simultaneously, and calcium formiate quality is as follows:
3, the waste liquid that the introduction such as Xiao Bolin is produced from oxammonium hydrochloride, add in calcium carbonate and in waste water 10%～15% formic acid, prepare calcium formiate.
4, the report such as Qiqihar chemical general factory Chen Zhen recovery calcium formiate from chloroform alkaline hydrolysis is residual, calcium formiate content is 91.5%～94.2%.
5, Sun Baoyuan etc. for invention in calcium carbonate, calcium hydroxide and formic acid prepare calcium formiate (CN1472186/A).
6, the invention such as Li Zhi's light utilizes calcium formiate and nitrocalcite or calcium nitrite replacement(metathesis)reaction to prepare calcium formiate, simultaneously by-product sodium nitrate or Sodium Nitrite (CN101239896/A).
7, calcium hydroxide generates calcium formiate with formaldehyde reaction under catalyst action, also wants separation of methanol: Ca (OH) simultaneously
2+ 4HCHO → Ca (HCOO)
2+ 2CH
3oH.
USSR (Union of Soviet Socialist Republics) 1474157 patents, by add manganous sulfate, ferrous sulfate, calcium chloride, nitrocalcite, stopper in reaction solution, can be increased to 85% by the yield of calcium formiate, do not possess industrial production and are worth.
8, German Degussa AG company adopts calcium hydroxide, formaldehyde, hydrogen peroxide (mol ratio 1:1:1.2) or with calcium oxide and formaldehyde (mol ratio 1:2) reaction production calcium formiate, reaction formula is:
Ca(OH)
2+2HCHO+H
2O
2→Ca(HCOO)
2+2H
2O+H
2
CaO+2HCHO+H
2O→Ca(HCOO)
2+2H
2
40 ℃～50 ℃ of temperature of reaction, need violent stirring, in 45 minutes reaction times, use ZrCI
4suppress the saccharification of formaldehyde, reaction end pH value 6.5～7.5, calcium formiate yield 97%, purity 99.7%, because production cost is too high, has no industry report.
9, the military red outstanding person of University Of Tianjin etc. is in 0.5 liter reactor, with calcium hydroxide and carbon monoxide carbonyl compound formic acid calcium, and 180 ℃ of temperature of reaction, 600 revs/min of stirring velocitys.Carbon monoxide and calcium hydroxide initial molar ratio are greater than 3:1, pressure 5MPa, and in 20 minutes reaction times, calcium formiate content can be greater than 97%.
10, Luo Zongtian once introduced the carbonylating process that United States Navy Department has developed a kind of calcium hydroxide, and its object is hydrogen manufacturing, belonged to secrecy technology, and patent is not given open, and principle is as follows:
Ca(OH)
2+2CO→Ca(HCOO)
2
Ca(HCOO)
2→CaCO
3+H
2+CO(300-400℃)。
11, Zeng Zhouhua, Zhang Shengli are at CN201517076, and CN102240529 has proposed CO and the synthetic calcium formiate of calcium hydroxide downflow system tubular reactor.
12, Cao Zhengxiang, Cao Yong have introduced by Ca (OH) in ZL20082014570.0
2produce continuously the technology and equipment with calcium formiate with CO.
China is maximum in the world calcium carbide and phosphorus production state, approximately 900,000 tons of the yellow phosphorus annual production of China at present, 1 ton of yellow phosphorus of every production can by-product containing the tail gas 2500～3000Nm of carbon monoxide (CO) approximately 80%～95%
3, approximately 1,800 ten thousand tons of the calcium carbide annual production of China, 1 ton of calcium carbide of every production can by-product containing electric furnace stone tail gas (also claiming calcium carbide tail gas) 400～600Nm of CO 77%～90%
3.And produce 10000 tons of food grade calcium formiates per year, only need approximately 4,700,000 Nm
3yellow phosphorus or calcium carbide tail gas.At present China can be for the yellow phosphorus utilizing and calcium carbide tail gas up to 9,400,000,000 Nm
3.Approximately 1.5 hundred million tons of China's feed annual production, if add 1% calcium formiate in its feed, approximately 1,500,000 tons of the potential annual requirements of calcium formiate, when electricity consumption acetylene made of stones, 1 ton of calcium carbide of every consumption can produce containing 96% Ca (OH)
2approximately 1 ton of carbide slag, the whole nation can produce nearly 1,800 ten thousand tons of carbide slags every year, is almost waste, contaminate environment not only, and have larger waste.
Summary of the invention
The object of the invention is to overcome above-mentioned deficiency, a kind of method of utilizing carbide slag and the synthetic calcium formiate of carbon monoxide is provided, the method not only can fully utilize the industrial three wastes and by-product, and can prepare the calcium formiate product of food grade, and the reaction times is short, cost is low, can less environmental pollution, comprehensive benefit is high.
The object of the present invention is achieved like this:
A kind of method of utilizing carbide slag and the synthetic calcium formiate of carbon monoxide, the method is utilized the carbide slag by calcium carbide legal system acetylene, and the synthetic calcium formiate of carbon monoxide of yellow phosphoric tail gas or calcium carbide stove exhaust or the acquisition of other approach, first by carbide slag pre-treatment, through changing slurry, filtering screening, pulverize, then, with the yellow phosphoric tail gas of purification or carbon monoxide process countercurrent reaction in reaction tower of the carbon monoxide in calcium carbide stove exhaust or the acquisition of other approach, obtain food grade calcium formiate.
Carbide slag must react the carbide slag (main component is calcium hydroxide) generating by newborn calcium carbide with water, change after starching and isolate the impurity such as ferrosilicon that particle diameter is larger, then pulverizing makes calcium hydroxide particle diameter be less than 200 orders, is preferably less than 320 orders, Ca (OH)
2working concentration best 8%～10%.
By-product carbon monoxide (CO) can adopt the yellow phosphoric tail gas of CO content 80%～95%, also can adopt the calcium carbide stove exhaust (also claiming calcium carbide tail gas) of CO content 77%～90%, and these tail gas are the separation H harmful to equipment preferably
2s, SO
2, PH
3, P
4deng.Work as O
2content is less than 0.5% and can process.CO
2can not process.
Calcium formiate is synthetic can adopt tower or tubular reactor, and the feature of this reactor is that the calcium hydroxide of content 8%～10% and circulating reaction liquid are sprayed into by tower top (or pipe top).The CO of take is main calcium carbide stove exhaust or yellow phosphoric tail gas, enters reactor carry out reverse-flow reaction with calcium hydroxide or reaction solution after compressor compression by the bottom of tower (or pipe).System response pressure is 3～6MPa, and preferably 4.1～5MPa, is preferably 4.5 MPa, 150～200 ℃ of temperature of reaction, best 160～200 ℃.20 minutes～2 hours reaction times.
8%～10% calcium hydroxide dispersion and circulation fluid atomization spray in reactor, can one-level, and also can be multistage.
In reactor, can use sieve-tray tower, tray column, mesh tower, rotating stream tray scrubber or mix the column plate of pattern.Reaction can single tower, also can adopt multitower.When batch production, can adopt single tower.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention utilizes the industrial three wastes (carbide slag) and by-product (yellow phosphorus or calcium carbide are produced the tail gas containing CO) synthesised food level calcium formiate.The method not only can fully utilize the industrial three wastes and by-product, and product purity is high, can directly prepare the calcium formiate product of food grade, in addition, adopts counter-current to produce, and the reaction times is short.Whole reaction process cost is low, can less environmental pollution, and comprehensive benefit is high.
Accompanying drawing explanation
Fig. 1 is calcium carbide stove exhaust processing flow chart;
Fig. 2 is yellow phosphoric tail gas processing flow chart;
Fig. 3 is calcium formiate batch production schema;
Fig. 4 is thick calcium formiate aftertreatment flow process;
Fig. 5 is calcium formiate continuous processing production scheme.
Embodiment
Embodiment 1: calcium formiate batch production method
First, by newborn carbide slag, under agitation add aquation and become Ca (OH)
2the slurry of content 11% left and right, removes by filter with 100 mesh sieves the impurity that particle diameter is larger, and particle diameter is less than 100 object Ca (OH)
2,through pulverizing, then filter through 325 eye mesh screens, get filtrate, make Ca (OH)
2it is 8%～10% standby that content reaches.The object of filtering is to be conducive to calcium formiate synthesize, and also protects dehvery pump and recycle pump.
Calcium carbide and/or yellow phosphoric tail gas are removed dust and HF, SO
2, H
2s, P
4, PH
3deng detrimental impurity, so must carry out pre-treatment.Although some impurity does not affect the preparation quality of calcium formiate, can corrode the equipment such as compressor.CO
2although can consume Ca (OH)
2, but be CaCO due to what generate
3precipitation, is easy to separated with water miscible calcium formiate.When in tail gas, oxygen level is less than 0.5%, O
2can not process.
Calcium carbide tail gas treating processes is as shown in Figure 1: calcium carbide tail gas, after wet dedusting cooling, demist, supercharging, washing, alkali cleaning, is obtained to CO gas;
Phosphorus production is in order to reduce costs conventional coal manufacture-yellow phosphorus, and high sulphur coal often causes containing in yellow phosphoric tail gas H
2s, SO
2with other sulfide, yellow phosphoric tail gas treating processes as shown in Figure 2: yellow phosphoric tail gas is obtained to CO gas through wet type cooling, demist, supercharging, desulfurization, alkali cleaning;
When with the synthetic calcium formiate of carbide slag, CO
2can generate insoluble CaCO with lime reaction
3, but can not have a strong impact on the quality of calcium formiate.
Calcium formiate batch production flow process is as shown in Figure 3:
8%～10% Ca (OH) processing
2after metering, by high-pressure pump 1, through interchanger 2, be warming up to more than 150 ℃, by spraynozzle 3.1, spray into synthetic tower 3.Synthetic tower 3 can be void tower, also can use sieve-tray tower, tray column, mesh tower, rotating stream tray scrubber, or the column plate of mixed type, in batch production, can use single tower, also can double tower or multitower.The single tower of general use.Purify CO gas through four-stage compressor 4 compressions, by entering synthetic tower by synthetic tower 3 bottoms 3.2 after interchanger 5 preheatings, and reach control pressure.Synthetic tower 3 starts recycle pump 6.1 or 6.2 while heating up, sprayed in tower through interchanger 7 is laggard, simultaneously Ca (OH) by synthetic tower 3 top nozzles 3.4
2react with CO in tower.Reaction pressure 1.6～6MPa, also can be used higher CO pressure, although the reaction times can shorten, facility investment increases, and power consumption increases and uneconomical.150～180 ℃ of temperature of reaction, higher temperature also can be reacted, and can Reaction time shorten, but infeasible because increasing the corrosion of equipment and may destroying the stability in use of recycle pump.When batch production, the pressure of synthetic tower 3 can be stablized certain pressure and react, and also can maintain certain pressure and react above.When synthetic tower 3 pressure no longer reduce, reaction finishes, can be in synthetic tower 3 thief hole 3.5 samplings, and assaying reaction liquid pH, when pH reaches 7～8, calcium formiate is synthetic to be finished immediately, 20 minutes to 2 hours reaction times.Reaction solution (being thick calcium formiate) is put into tundish after interchanger 8 coolings, then after Fig. 4 flow processing, can obtain the calcium formiate product of food grade.
Ca (OH) as shown in Figure 3
2, CO and circulation fluid interchanger 2,5,7 can use thermal oil or superheated vapo(u)r heating, calcium formiate interchanger 8, emptying CO interchanger 9 can use circulating water cooling.
Fig. 4 flow process is: thick calcium formiate is through filtration, membrane filtration, condensing crystal, the high-purity calcium formiate through filtering again, and then through the finished product calcium formiate of super-dry, packing.
Calcium formiate is solubleness approximately 14% at normal temperatures, as Ca (OH)
2content is greater than 9%, calcium formiate content can be greater than 15%, for fear of calcium formiate, bring in throw out, calcium formiate as thick in Fig. 4 adds washing and filtering water, and controlled concentration, in 15% left and right, can be used centrifuging or press filtration, after filtrate supernatant again through membrane filtration, calcium formate solution through membrane filtration can adopt the dehydration of efficient concentration crystallizer, and after filtration, calcium formiate crystallizing and drying can obtain the food grade calcium formiate that calcium formiate content is greater than 99%.
Owing to consuming CO in reaction, after reaction, CO content can decline, and the lower concentration CO gas therefore discharging in batch production can be used as fuel and uses.
Intermittent type calcium formiate is produced and is suitable for small-scale calcium formiate production.
Concrete grammar is:
12m
3sieve-tray tower is warming up to 175 ℃, is pressed into the yellow phosphoric tail gas through purifying, 9.6% Ca (OH) that adds carbide slag to obtain after treatment
2circulating reaction, maintains system pressure 4.0MPa, reacts after 35 minutes, goes out pH7～8 of tower calcium formiate, obtains the aqueous solution of calcium formiate content approximately 15.8%, through cooling, filter, concentrated, crystallization, the dry calcium formiate that to obtain, measurement result is as follows:
Ca in reaction (OH)
2transformation efficiency 99%.A small amount of hydrogen-oxygen calcium is converted into CaCO
3.
Embodiment 2: calcium formiate continuous processing working system
By the method for embodiment 1, carbide slag is carried out to pre-treatment, obtain 8%～10% Ca (OH)
2solution;
The treatment process of calcium carbide and/or yellow phosphoric tail gas is also same with embodiment 1.
Reaction process is referring to Fig. 5,8%～10% Ca (OH) of processing
2after metering, by high-pressure pump 1, after interchanger 2 heat exchange, by synthetic tower 3/A top, through spraynozzle 3A1, spray into synthetic tower 3/A, from the CO gas of synthetic tower 3/B, through 3A2, enter synthetic tower 3/A and Ca (OH) from tower top
2carry out backward reaction with circulation fluid, reacted CO gas is discharged by synthetic tower 3/A tower top, and most of CO is mixed into synthetic tower 3/C with the CO from compressor 4 preheating after being compressed by recycle compressor 10 after mist eliminator 11 demists.In order to ensure the concentration of synthetic tower CO, by part lower concentration CO gas after interchanger 9 cooling to gas holder as fuel.The reaction solution of synthetic tower 3/A is controlled certain liquid level at synthetic tower 3/A, and by draw-off pump 12A, will surpass liquid level reaction solution and drain into reaction tower 3/B, and most of reaction solution is by being sprayed into and carried out anti-phase with CO gas in reaction tower 3/A and react by nozzle 3A4 through recycle pump 6/A at the bottom of 3/A tower.When synthetic tower 3/A temperature is lower than controlling temperature, circulation fluid enters reaction tower 3/A after interchanger 7A preheating.The reaction solution that reaction obtains is transported to reaction tower 3/B by draw-off pump 12, and sprays into reaction tower 3/B through nozzle 3B1 atomization, carries out backward reaction with the CO from reaction tower 3/C.3/A is identical with reaction tower, higher than reaction tower 3/B, controls liquid level, and unnecessary reaction solution is transported to reaction tower 3/C by draw-off pump 12B by calcium formiate and unreacted calcium hydroxide and reacted at reaction tower 3/C anti-phase with CO gas.Control reaction tower 3/C and go out tower liquid pH7～9, preferably pH7～8.In production, control too the liquid level of reaction tower 3/C, in the situation that guaranteeing reaction liquid level, discharge completely reacted calcium formiate reaction solution, after interchanger 8 is cooling, carry out aftertreatment.
Calcium formiate successive reaction tower structure is identical with rhythmic reaction tower structure, and successive reaction should strictly be controlled temperature of reaction, pressure, Ca (OH)
2input concentration and inlet amount and CO input concentration and inlet amount.The strict control reaction times.Reaction tower can be 3, can be also a plurality of, and preferably 4～5, the pH value that goes out tower liquid is less than 8.
Concrete grammar is:
4 12m
3sieve-tray tower series connection, 175 ℃ of control tower temperature, countercurrent reaction, pressure 4.5MPa, carbide slag obtains calcium hydroxide content 9.58% after treatment, theoretical 30 minutes residence time of calcium hydroxide, go out tower calcium formiate pH8, calcium hydroxide transformation efficiency 99% is adjusted pH to 7 with a small amount of formic acid after cold filtration.Filter, concentrated, crystallization, the dry quicksand shape calcium formiate that to obtain, quality is as follows:
Carbon monoxide per pass conversion is greater than 80%.
Claims (9)
1. a method of utilizing the synthetic calcium formiate of carbide slag and carbon monoxide, it is characterized in that: the method utilization is by the carbide slag of calcium carbide legal system acetylene, and the synthetic calcium formiate of carbon monoxide of yellow phosphoric tail gas or calcium carbide stove exhaust or the acquisition of other approach, first by carbide slag pre-treatment, through changing slurry, filtering screening, pulverize, then, with the yellow phosphoric tail gas of purification or carbon monoxide process countercurrent reaction in reaction tower of the carbon monoxide in calcium carbide stove exhaust or the acquisition of other approach, obtain calcium formiate.
2. the method for utilizing the synthetic calcium formiate of carbide slag and carbon monoxide according to claim 1, it is characterized in that, described carbide slag preprocessing process is: after changing slurry, isolate the impurity that particle diameter is larger, then pulverizing makes calcium hydroxide particle diameter be less than 200 orders, and regulate concentration, make Ca (OH)
2concentration adjustment to 8%～10%.
3. the method for utilizing carbide slag and the synthetic calcium formiate of carbon monoxide according to claim 2, is characterized in that, after pulverizing, calcium hydroxide particle diameter is less than 320 orders.
4. the method for utilizing carbide slag and the synthetic calcium formiate of carbon monoxide according to claim 1, is characterized in that, the carbon monoxide of employing adopts the yellow phosphoric tail gas of CO content 80%～95%, or adopts the calcium carbide stove exhaust of CO content 77%～90%.
5. the method for utilizing the synthetic calcium formiate of carbide slag and carbon monoxide according to claim 1, it is characterized in that, calcium formiate is synthetic can adopt tower or tubular reactor, this reactor is, the calcium hydroxide of content 8%～10% and circulating reaction liquid are entered by tower top or pipe top spray, take CO as main calcium carbide stove exhaust or yellow phosphoric tail gas, after compressor compression, by the bottom of tower or pipe, enter reactor and carry out reverse-flow reaction with calcium hydroxide or reaction solution, system response pressure is 3～6MPa, 150～200 ℃ of temperature of reaction, 20 minutes～2 hours reaction times.
6. the method for utilizing carbide slag and the synthetic calcium formiate of carbon monoxide according to claim 5, is characterized in that, system response pressure is 160～200 ℃ of 4.1～5MPa temperature of reaction.
7. the method for utilizing carbide slag and the synthetic calcium formiate of carbon monoxide according to claim 1, is characterized in that, 8%～10% calcium hydroxide dispersion and circulation fluid atomization spray in reactor.
8. the method for utilizing carbide slag and the synthetic calcium formiate of carbon monoxide according to claim 1, is characterized in that, the synthetic method batch production of calcium formiate, or adopt continous way to produce.
9. the method for utilizing carbide slag and the synthetic calcium formiate of carbon monoxide according to claim 1, is characterized in that, described calcium carbide tail gas treating processes is: calcium carbide tail gas, after wet dedusting cooling, demist, supercharging, washing, alkali cleaning, is obtained to CO gas; Described yellow phosphoric tail gas treating processes is: yellow phosphoric tail gas is obtained to CO gas through wet type cooling, demist, supercharging, desulfurization, alkali cleaning.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664571A (en) * | 2013-12-25 | 2014-03-26 | 云南省化工研究院 | Method for synthesizing calcium formate by using industrial emission carbon monoxide exhaust gas through batch reaction |
| CN109422641A (en) * | 2017-09-05 | 2019-03-05 | 天津大学 | The continuous producing method of calcium formate is prepared by yellow phosphoric tail gas |
| CN109879747A (en) * | 2019-04-01 | 2019-06-14 | 辽宁赛菲化学有限公司 | A kind of method of carbide slag production calcium formate |
| CN116119701A (en) * | 2023-03-16 | 2023-05-16 | 河北工业大学 | Method for preparing nano calcium carbonate from carbide slag |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475463A (en) * | 2009-01-21 | 2009-07-08 | 曹勇 | Method for coproduction of high purity aminic acid and acid sodium phosphate by reaction of calcium formate and peroxyphosphoric acid |
| CN201325936Y (en) * | 2008-12-16 | 2009-10-14 | 曹勇 | Calcium formate preparation device by continuous carbonylation of carbon monoxide and calcium hydroxide |
| CN101880223A (en) * | 2010-06-29 | 2010-11-10 | 濮阳市银泰新型建材有限公司 | Method for preparing calcium formate from carbon monoxide and calcium hydroxide |
| CN103113208A (en) * | 2013-02-27 | 2013-05-22 | 天津大学 | Continuous production process for preparing calcium formate through calcium hydroxide carbonylation |
-
2013
- 2013-07-08 CN CN201310281962.4A patent/CN103601630A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201325936Y (en) * | 2008-12-16 | 2009-10-14 | 曹勇 | Calcium formate preparation device by continuous carbonylation of carbon monoxide and calcium hydroxide |
| CN101475463A (en) * | 2009-01-21 | 2009-07-08 | 曹勇 | Method for coproduction of high purity aminic acid and acid sodium phosphate by reaction of calcium formate and peroxyphosphoric acid |
| CN101880223A (en) * | 2010-06-29 | 2010-11-10 | 濮阳市银泰新型建材有限公司 | Method for preparing calcium formate from carbon monoxide and calcium hydroxide |
| CN103113208A (en) * | 2013-02-27 | 2013-05-22 | 天津大学 | Continuous production process for preparing calcium formate through calcium hydroxide carbonylation |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664571A (en) * | 2013-12-25 | 2014-03-26 | 云南省化工研究院 | Method for synthesizing calcium formate by using industrial emission carbon monoxide exhaust gas through batch reaction |
| CN103664571B (en) * | 2013-12-25 | 2016-03-09 | 云南省化工研究院 | A kind of method of industrial discharge carbon monoxide tail gas intermittent reaction synthesis calcium formiate |
| CN109422641A (en) * | 2017-09-05 | 2019-03-05 | 天津大学 | The continuous producing method of calcium formate is prepared by yellow phosphoric tail gas |
| CN109879747A (en) * | 2019-04-01 | 2019-06-14 | 辽宁赛菲化学有限公司 | A kind of method of carbide slag production calcium formate |
| CN116119701A (en) * | 2023-03-16 | 2023-05-16 | 河北工业大学 | Method for preparing nano calcium carbonate from carbide slag |
| CN116119701B (en) * | 2023-03-16 | 2024-04-26 | 河北工业大学 | Method for preparing nano calcium carbonate from carbide slag |
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Application publication date: 20140226 |