CN102924257A - Method for preparing high-purity sodium formate by using tail gas of synthesis ammonia liquid nitrogen wash device - Google Patents
Method for preparing high-purity sodium formate by using tail gas of synthesis ammonia liquid nitrogen wash device Download PDFInfo
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- CN102924257A CN102924257A CN2012103796926A CN201210379692A CN102924257A CN 102924257 A CN102924257 A CN 102924257A CN 2012103796926 A CN2012103796926 A CN 2012103796926A CN 201210379692 A CN201210379692 A CN 201210379692A CN 102924257 A CN102924257 A CN 102924257A
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Abstract
The invention provides a method for preparing high-purity sodium formate by using tail gas of a synthesis ammonia liquid nitrogen wash device. The method comprises the following steps that: the tail gas generated by the synthesis ammonia liquid nitrogen wash device is compressed to a proper pressure by a compressor, the compressed tail gas is mixed with sodium hydroxide liquid conveyed by using a liquid alkaline pump, and the mixture is preheated and then enters a synthesis reactor to react to generate qualified diluted sodium formate; and the generated diluted sodium formate solution is concentrated in an evaporating manner, centrifugally separated and dried with air to obtain the high-purity sodium formate with the purity being above 99 percent. The method provided by the invention solves the problem that the tail gas of the synthesis ammonia liquid nitrogen wash device is used as a combustion gas, is low in recycling value and pollutes the environment, and solves the defects of lagging production equipment of the traditional sodium formate production process, high production cost caused by using coke or lump coal as a raw material, environment pollution, small yield, low purity of the sodium formate, and the like, and has the advantages of low energy consumption, low production cost, high purity of the sodium format, large scaling, no pollution and adjustable yield.
Description
Technical field
The present invention relates to the synthetic field of fine chemistry industry material, be specifically related to utilize synthetic ammonia liquid nitrogen washing device tail gas to prepare the method for high-purity sodium formate.
Background technology
Sodium formiate chemical formula HCOONa2H2O, molecular weight 104.04.Density 1.919g/cm3.The formic acid smell is slightly arranged.Soluble in water and glycerine is slightly soluble in ethanol.253 ℃ of fusing points.The industry sodium formiate is usually used in leather industry, the camouflage acid in the chromium tanning; Be used for catalyzer and stable compound agent; The reductive agent of dyeing; Also for the production of vat powder, oxalic acid and formic acid; Also be widely used in recent years the early strong oil field drilling fluids that reaches preparation low toxicity, environmental protection of cement.
At present, the processing method of production sodium formiate mainly contains:.
(1) neopentyl glycol absorption method and tetramethylolmethane absorption method.
These two kinds of recovery methods are respectively the sodium formiate byproduct that produces in neopentyl glycol production process and the Production of pentaerythritol process to be recycled, its output is subjected to the restriction of neopentyl glycol or tetramethylolmethane output, and the organic impurities content in the product is higher, sodium formiate purity is generally about 94%, difficult quality control has influence on the application of product.
(2) utilize semi-water gas (or dry gas) to produce the processing method of sodium formiate.
The method is utilized producer gas generator, adopting coke or lump coal is raw material, generation contains dry gas or the semi-water gas of carbon monoxide about 30%, after removing the impurity such as hydrogen sulfide, carbonic acid gas, the operations such as cooling dedusting, desulfurization, decarburization enter the gas compressor supercharging, carbon monoxide in the coal gas and sodium hydroxide solution enter synthetic tower and carry out building-up reactions generation sodium formiate, obtain industrial sodium formiate product behind evaporation concentration, centrifugation, air stream drying.This technique sodium formiate purity in the product for absorption method is slightly high, do not contain other alcohols, slightly high for the production of formic acid, vat powder yield, but, make raw material owing to adopt higher coke or the lump coal of price, fixed bed coal gas producer gas processed, processing unit is comparatively backward, consume high, production cost is high, foreign matter content is high in the product, other composition in the gas can not effectively utilize, desulfurization and decarbonization process can produce waste gas or waste liquid, environment there is certain pollution, single covering device throughput is little, should not install maximization, and unit production capacity facility investment is large.
Summary of the invention
The present invention utilizes synthetic ammonia liquid nitrogen washing device tail gas to prepare the method for high-purity sodium formate, it is co-producing high-purity sodium formiate product on the basis of original Large-scale Ammonia Plant production equipment, do not change, do not increase any equipment and the technique of former synthetic ammonia installation, and the tail gas that contains carbon monoxide 33%-50% that purified synthesis gas operation liquid nitrogen washing device is desorbed is as unstripped gas, carbon monoxide in the tail gas under certain temperature and pressure with sodium hydroxide solution generation building-up reactions, produce high-purity sodium formate.This technique had both solved synthetic ammonia installation liquid nitrogen washing tail gas only utilizes the low and contaminate environment of recovery value as burning gas problem, solved again that existing sodium formiate production process equipment falls behind, coke or many weak points such as lump coal is made raw material production cost height, contaminate environment, device capbility is little, product purity is low, provide that a kind of energy consumption is low, production cost is low, product purity high (sodium formiate content can reach more than 99%), device maximization, non-environmental-pollution, output can be according to the flexible production methods of the high-purity sodium formate of adjustment of the market requirement.
Reaction mechanism: the reaction under the condition of heating, pressurization of the carbon monoxide in the liquid nitrogen washing tail gas and sodium hydroxide solution generates sodium formiate:
The present invention adopts following technical scheme for achieving the above object:
1, utilize synthetic ammonia liquid nitrogen washing device tail gas to prepare the method for high-purity sodium formate, it is characterized in that: concrete steps are as follows:
(1) a certain amount of 32% ion film caustic soda is put into joined the alkali groove, add again a certain amount of technique soft water (or steam condensate of system recoveries), leave standstill after stirring, requirement, leaving standstill rear NaOH strength of solution is 180-230g/L, sedimentation time 8-10 hour;
(2) will precipitate qualified NaOH solution, squeeze in the diluted alkaline tank;
(3) liquid nitrogen washing tail gas is compressed to 1.8-2.2MPa through Qi Ti Ya Shrink machine;
(4) after the dilute alkaline soln that step (2) is configured is pressurized to 2.3-2.7MPa, jointly enters mixing tank with liquid nitrogen washing tail gas after step (3) compression and mix;
(5) allow the mixed mixture of step (4) advance the preheater preheating after, enter synthesis reactor, generate dilute formic acid sodium in the synthesis reactor reaction, requirement, preheating temperature is 150-170 ℃, synthesis temperature 170-190 ℃, the volumetric concentration of volumetric concentration 〉=360g/L of NaCOOH, NaOH is 2-6g/L in the dilute formic acid sodium;
(6) the dilute formic acid sodium of step (5) generation becomes dense sodium formate solution after I single-effect evaporator and II single-effect evaporator evaporation concentration; Requirement, II single-effect evaporator vacuum tightness-0.06 Mpa～-0.08Mpa, control II single-effect evaporator concentrated solution solid-liquid is than about 20%, to save steam;
(7) the dense sodium formate solution of step (6) gained is through wet cyclone fractional crystallization body, clear liquid returns the II single-effect evaporator, advances dense sodium formiate storage tank with the dense sodium formate solution of mass crystallization, then is sent from the heart and separates the post, requirement, solid-to-liquid ratio is more than 60% in the dense sodium formiate liquid;
(8) with the dense sodium formiate liquid centrifugation after step (7) evaporation concentration, isolate solid sodium formate;
(9) with the isolated solid sodium formate of step (8), pack after the drying and namely obtain the high-purity sodium formate product.
The described method of utilizing synthetic ammonia liquid nitrogen washing device tail gas to prepare high-purity sodium formate is characterized in that: the purity of the described high-purity sodium formate of step (9) 〉=99%.
Beneficial effect of the present invention:
(1) the present invention utilizes the End gas production high purity of liquid nitrogen washing device by-product, the sodium formiate product of high added value, has solved the only difficult problem of, contaminate environment low as burning gas burning utility value of liquid nitrogen washing tail gas in the Large-scale Ammonia Plant technology;
(2) because Mass Synthetic Ammonia Unit adopts advanced pressurized gasification technology, adopt the lower bunker coal of price as raw material, adopt coke to fall behind, can not realize that as raw material, equipment maximization, the dumb production cost of comparing of Load Regulation decline to a great extent with lump coal with existing sodium formiate production technology, but the simultaneously maximization of implement device, producing load can be according to the market situation flexible;
(3) production process non-pollutant discharge has solved the problem of existing production technique contaminate environment;
(4) high-purity sodium formate produced of the present invention has solved that the sodium formiate product impurity that existing production technique produces is many, purity is low, and the difficult problem that Application Areas is limited has improved product specification;
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
Referring to accompanying drawing, provide the specific embodiment of the present invention:
The key equipment table look-up
| Sequence number | Title | Specification | Quantity |
| 1 | Ya Shrink machine | 60m 3/min | 3 |
| 2 | Well heater | Heat interchanging area 200m 2 | 2 |
| 3 | Synthesis reactor | DN600、DN400 | 32 |
| 4 | Vaporizer | Heat interchanging area 400m 2 | 2 |
The production equipment of producing 300000 tons of synthetic ammonia per year take a cover is as example, according to the market situation of sodium formiate by regulating CO content after the conversion, its purified synthesis gas operation liquid nitrogen washing device parse tail gas, can coproduction 2～50,000 ton/year high-purity sodium formate.
Utilize synthetic ammonia liquid nitrogen washing device tail gas to prepare the processing method of high-purity sodium formate, technical process is: the 0.12MPa that is transported by Large-scale Ammonia Plant refining plant liquid nitrogen washing operation, 30 ℃ contain CO33%-50%(all the other are mainly nitrogen) tail gas advance three grades of piston-type non-lubricated gas compressors through surge tank and be forced into 1.8-2.2 MPa, the certain density liquid sodium hydroxide that comes with the high pressure base pumping mixes, after being heated to 150-175 ℃, heater via in synthesis reactor, carries out building-up reactions, generate qualified dilute formic acid sodium, through gas-liquid separation, evaporation concentration, centrifugation, the high-purity sodium formiate of finished product behind the air stream drying is packed, and the main component after the gas-liquid separation is the tail gas emptying of nitrogen.Concrete steps are as follows:
Join the alkali operation
1, puts into a certain amount of 32% ion film caustic soda to joining the alkali groove, add again a certain amount of soft water (or steam condensate) to stipulating scale, after opening stirring, mixing, sampling analysis, the NaOH strength of solution is 180-230g/L, and content is defective to add NaOH or soft water again, until analyze qualified, squeeze into the diluted alkaline groove with pump, according to the about 200m of the every well matched foot of the condition of production
3About, and evenly preparation.
2, after the diluted alkaline preparation, ensure 8 hours precipitations.
3, forbid the diluted alkaline of preparation is squeezed in the diluted alkaline tank that is using.
The compression synthesis procedure
1, main task is that tail gas entrance pressure Shrink machine after buffering that the liquid nitrogen washing operation is sent here is forced between 1.8～2.2MPa, and the diluted alkaline that comes with the high pressure base pumping mixes mutually, after the heater via heating in reactor step reaction generate dilute formic acid sodium.Dilute formic acid sodium advances dilute formic acid sodium storage tank after spinning liquid separates, and unacceptable product is returned stream, returns and joins the alkali pond.
2, open the compressor intake valve, starting compressor checks oil pressure and hydraulic pressure.Drive outlet valve, close blow-off valve, liquid nitrogen washing tail gas is sent into synthesis system.
3, open steam valve, send steam heating to well heater.
4, off-response device outlet valve.
5, open the outlet valve of diluted alkaline tank, the terminal valve of alkali pump.
6, start alkali pump, regulate variable valve to required flow.
7, when system pressure rises to 1.8Mpa, open gradually outlet valve, the synthetic tower intake pressure is stabilized between 1.8 ~ 2.2Mpa.
8, the sampling analysis product qualified after, product is sent into dilute formic acid sodium basin, unacceptable product is returned stream, returns and joins the alkali pond.
9, synthesis pressure is stabilized in 1.8～2.2MPa, and top hole pressure is stabilized in 0.5～1.5MPa.
Evaporation concentration is separated drying process
1, main task is that the dilute formic acid sodium of handle 〉=360g/L is pressed into the two-effect evaporation device, and evaporation concentration is packed behind centrifugation, air stream drying to the sodium formiate crystallization.
2, from dilute formic acid sodium storage tank to I single-effect evaporator feed, I effect steam send II effect heating chamber, automatically imitate punishment in advance from the I effect to II according to II single-effect evaporator liquid level, the steam water inlet power that the II single-effect evaporator produces is sprayed pumped vacuum systems and is recycled the water absorption, dense sodium formate solution after the evaporation of II effect is evacuated to wet cyclone fractional crystallization body through adopting salt pump, clear liquid returns the II single-effect evaporator, advances dense sodium formiate storage tank with the dense sodium formate solution of mass crystallization;
3, according to height of liquid level, automatically controlled valve is adjusted quantity of reflux and inlet amount, makes an effect level stability.For preventing that automatically control is malfunctioning, operator will often observe liquid level and in time replenish liquid level with dilute formic acid sodium liquid level is remained between the upper and lower visor.The 2nd effect evaporator liquid level increases liquid level with evaporation time and descends, and the liquid level automatic regulating valve is imitated punishments in advance from 1st effective evaporator to two automatically according to the 2nd effect evaporator liquid level change.
4, treat that sodium formiate is concentrated to solid crystal and opens greater than 20% the time approximately and adopt salt pump, gather the dense sodium formate solution that contains crystallization from the 2nd effect evaporator bottom, send wet cyclone to separate, clear liquid returns two effect evaporator rooms, and end liquid advances dense sodium formiate receiving tank.
5, dense sodium formiate slip is delivered to whizzer, carry out centrifugation, mother liquor advances the mother liquor accumulator tank, returns 2nd effect evaporator with the mother liquor pump and continues evaporation.
6, the wet feed after centrifugal carries out metering packing behind air stream drying.
Main technique index in the present embodiment:
1, liquid nitrogen washing tail gas pressure, temperature: 0.08-0.12MPa, 30-35 ℃;
2, CO content was at 0.6-1.8% after liquid nitrogen washing tail gas CO content 33-50%(adjusted conversion flexibly according to throughput requirements);
3, compressor delivery pressure 1.8-2.2 MPa;
4, heater outlet temperature: 150-175 ℃;
5, join alkali lye NaOH content 180-200g/l;
6, dilute formic acid sodium content 〉=360 g/l
7, dilute formic acid sodium NaOH content 2-6 g/l
8, dual evaporation vacuum tightness 〉=0.06MPa;
9, dry product sodium formiate content 〉=99.0%.
Claims (2)
1. utilize synthetic ammonia liquid nitrogen washing device tail gas to prepare the method for high-purity sodium formate, it is characterized in that: concrete steps are as follows:
(1) a certain amount of 32% ion film caustic soda is put into joined the alkali groove, add again a certain amount of technique soft water (or steam condensate of system recoveries), leave standstill after stirring, requirement, leaving standstill rear NaOH strength of solution is 180-230g/L, sedimentation time 8-10 hour;
(2) will precipitate qualified NaOH solution, squeeze in the diluted alkaline tank;
(3) liquid nitrogen washing tail gas is compressed to 1.8-2.2MPa through Qi Ti Ya Shrink machine;
(4) after the dilute alkaline soln that step (2) is configured is pressurized to 2.3-2.7MPa, jointly enters mixing tank with liquid nitrogen washing tail gas after step (3) compression and mix;
(5) allow the mixed mixture of step (4) advance the preheater preheating after, enter synthesis reactor, generate dilute formic acid sodium in the synthesis reactor reaction, requirement, preheating temperature is 150-170 ℃, synthesis temperature 170-190 ℃, the volumetric concentration of volumetric concentration 〉=360g/L of NaCOOH, NaOH is 2-6g/L in the dilute formic acid sodium;
(6) the dilute formic acid sodium of step (5) generation becomes dense sodium formate solution after I single-effect evaporator and II single-effect evaporator evaporation concentration; Requirement, II single-effect evaporator vacuum tightness-0.06 Mpa～-0.08Mpa, control II single-effect evaporator concentrated solution solid-liquid is than about 20%, to save steam;
(7) the dense sodium formate solution of step (6) gained is through wet cyclone fractional crystallization body, clear liquid returns the II single-effect evaporator, advances dense sodium formiate storage tank with the dense sodium formate solution of mass crystallization, then is sent from the heart and separates the post, requirement, solid-to-liquid ratio is more than 60% in the dense sodium formiate liquid;
(8) with the dense sodium formiate liquid centrifugation after step (7) evaporation concentration, isolate solid sodium formate;
(9) with the isolated solid sodium formate of step (8), pack after the drying and namely obtain the high-purity sodium formate product.
2. the described method of utilizing synthetic ammonia liquid nitrogen washing device tail gas to prepare high-purity sodium formate according to claim 1 is characterized in that: the purity of the described high-purity sodium formate of step (9) 〉=99%.
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| CN103880040A (en) * | 2014-02-25 | 2014-06-25 | 中盐安徽红四方股份有限公司 | Exhaust gas recycling method for large ammonia liquid nitrogen washing device |
| CN104193611A (en) * | 2014-08-08 | 2014-12-10 | 烟台金海化工有限公司 | Co-production preparation method of sodium formate and methanol |
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Patent Citations (4)
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| CN101033183A (en) * | 2007-03-02 | 2007-09-12 | 张少华 | Process for producing sodium formate from carbonic oxide in synthesis ammonia raw material gas |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103880040A (en) * | 2014-02-25 | 2014-06-25 | 中盐安徽红四方股份有限公司 | Exhaust gas recycling method for large ammonia liquid nitrogen washing device |
| CN104193611A (en) * | 2014-08-08 | 2014-12-10 | 烟台金海化工有限公司 | Co-production preparation method of sodium formate and methanol |
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Application publication date: 20130213 |