CN1491931A - Process for preparing granular patassium formate and its pelletizing equipment - Google Patents
Process for preparing granular patassium formate and its pelletizing equipment Download PDFInfo
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- CN1491931A CN1491931A CNA031390226A CN03139022A CN1491931A CN 1491931 A CN1491931 A CN 1491931A CN A031390226 A CNA031390226 A CN A031390226A CN 03139022 A CN03139022 A CN 03139022A CN 1491931 A CN1491931 A CN 1491931A
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Abstract
The present invention belongs to the field of chemical production technology. Gaseous CO is led into potassium hydroxide solution, and through reaction at the conditions of 150-230 deg.c temperature and 1.7-4.0 MPa pressure, dilute solution of potassium formate is obtained. Further, the solution is evaporated at 150-200 deg.c and normal pressure, airflow cooled at 110-180 deg.c, crystallized and palletized to obtain potassium formate product. The pelletizing equipment includes one cylinder with material inlet in the top, inside gas nozzle connected to a tubular adsorber and material vibrator in the lower part; one spiral pressure conveyer connected to the bottom of the cylinder; and exhauster connected to the top opening of the cylinder via pipe. The preparation process of granular potassium formate has simple path, high potassium formate content in the product and controllable product granularity; and the novel pelletizing equipment may be used also for pelletizing other material.
Description
(1) technical field
The present invention relates to the preparation method and the granulating equipment thereof of potassium formiate, belong to carbonizer's production technical field.
(2) background technology
Potassium formiate is widelyd popularize application just abroad as international known products, is mainly used in the petroleum drilling industry, also is being studied application in some field of fine chemical in addition, for example Rubber Chemicals Industries, freezing industry.And still being in the popularization stage in the application of China's potassium formiate, application market will constantly enlarge.
The production of potassium formiate mainly contains three kinds of methods industrial: a kind of is that acid-base reaction is produced the potassium formiate product, and the product that this method is produced is purer, but price is very expensive, uses uneconomically as Industrial products, can only use as analytical reagent.Second method is the hydrochlorate production method, promptly produce the potassium formiate product with formic acid and salt of wormwood reaction, domestic production producer is utilizing this method to produce a small amount of potassium formiate product in the past few years always, then stopped production, and facts have proved that this method also was uneconomic as suitability for industrialized production in nearest 2 years because production cost is high.The third method is the method that potassium formiate is produced in metathesis, produce vitriolate of tartar earlier: Repone K and sulfuric acid reaction are produced vitriolate of tartar, produce potassium formiate with vitriolate of tartar and formic acid reaction again, operational path complexity, equipment corrosion be serious, surrounding enviroment are caused very big pollution, and suitability for industrialized production is also uneconomical, do not meet environmental requirement.
There is report to show to have in the laboratory potassium cyanide is heated to boiling produces potassium formiate,, can in industrial production, utilizes the suspection of this method value, also do not see the report that related industries is produced because potassium cyanide itself belongs to hypertoxic chemical.JP7714716 discloses and has a kind ofly produced potassium formiate product (by-product sodium formiate product simultaneously) with basic metal, carbonate, carbonic acid gas, hydrogen by the reaction of complexity in the Japanese documentation.Many, the complexity of purifying of the potassium formiate product impurity that this production technique is produced does not have big practical value.CN1273962A discloses a kind of synthesis technique of potassium formiate, but there is the deficiency of two aspects in this technology, and the one, higher to the purity requirement of raw material CO (carbon monoxide converter) gas, make to purify the cost height; The 2nd, the potassium formiate of this explained hereafter is a flaked product, and is mobile poor, is unfavorable for the industrial application of product.
The potassium formiate solid phase prod is convenient to transportation and is preserved, it is also convenient to use, therefore in the production of potassium formiate in order to make solid phase prod, often need to make the potassium formiate solution crystallization, because potassium formiate solubleness is the moisture absorption greatly and very easily, thereby the potassium formiate production industry is being perplexed in the crystallization of potassium formiate always, at present domestic to be used for potassium formiate crystalline equipment be pelleter: fusion potassium formiate liquid flows to the iron cylinder of refrigerative of rotation, be cooled and crystallization on cylinder, scrape by scraper, thus the sheet potassium formiate crystal product of system.But this method makes the potassium formiate product and is difficult to satisfy the requirement of user to potassium formiate shape of product and granularity.
(3) summary of the invention
The present invention is directed to the deficiency of potassium formiate production technique in the prior art, propose a kind of preparation method and granulating equipment thereof of granular potassium formiate, operational path is simple, and the product purity height can satisfy the needs of industrial application.
The preparation method of granular potassium formiate of the present invention, adopt CO (carbon monoxide converter) gas and potassium hydroxide solution 150 ℃～230 ℃, be higher than that building-up reactions makes potassium formiate product dilute solution under 1.7Mpa to the 4.0Mpa condition, make the particulate state potassium formiate through pervaporation, granulation.
The preparation method of granular potassium formiate of the present invention comprises the steps:
1. with mol ratio (1～3): 1 CO (carbon monoxide converter) gas feeds in the potassium hydroxide solution, 150 ℃-230 ℃, be higher than under 1.7Mpa to the 4.0Mpa condition building-up reactions 1.5～6 hours, make potassium formiate product dilute solution;
2. saturated with being evaporated under the above-mentioned potassium formiate product dilute solution normal pressure, get the potassium formiate liquid product;
3. above-mentioned potassium formiate liquid product is evaporated to molten state under 150 ℃～200 ℃, normal pressure, under 110 ℃～180 ℃ temperature, makes granular potassium formiate product by the granulation of air-flow crystallisation by cooling.
Above-mentioned potassium hydroxide solution concentration is at weight percent 5%-35%.
In order to make high-quality potassium formiate product, note the impurity of control raw material:
The CO (carbon monoxide converter) gas source is abundant, be that CO (carbon monoxide converter) gas all is rich in the tail gas of producing yellow phosphorus, the release gas in the production of synthetic ammonia, gas furnace gas making (comprising oxygen enrichment gas making) etc., after various purification styles, can be as the unstripped gas of producing potassium formiate.The content of carbon monoxide has no special requirements in the unstripped gas, but other impurity in the unstripped gas but will be controlled: oxygen level is less than 0.1%, and carbonic acid gas is less than 0.2%, and inorganic sulfur+organosulfur is less than 0.05PPM.The purpose of controlling other impurity is the effective assurance that improves the potassium formiate quality product, keeps the safety in production.
The potassium hydroxide product that potassium hydroxide solution uses ionic membrane method to produce, concentration of potassium hydroxide is controlled at weight percent 5%-35%.In order to guarantee to produce the high quality potassium formiate, the present invention uses the potassium hydroxide product of ionic membrane method production, and the potassium hydroxide product impurity that this method is produced is few.The concentration of potassium hydroxide solution is that the potassium hydroxide that can utilize ionic membrane method to produce is direct and reaction of carbon monoxide in theory, does not have industrial production to be worth but the reaction times is very long.Consider economy, the reasonableness factor of production, the present invention dilutes the back to finished product potassium hydroxide product and uses, and the concentration of potassium hydroxide after the dilution is at weight percent 5%-35%.
Certainly in order to reduce production costs, the potassium hydroxide product that also can adopt diaphragm process to produce, the potassium hydroxide product impurity that diaphragm process is produced is many, and the quality of the potassium formiate product that obtains is not really desirable.
Being reflected at more than 150 ℃ of CO (carbon monoxide converter) gas and potassium hydroxide solution can be carried out, and along with the rising of temperature, speed of response is accelerated.But safer for the economy, the production environment that guarantee production process easy handling, system operation, product impurity is few, temperature of reaction of the present invention is controlled between 150 ℃-230 ℃.
CO (carbon monoxide converter) gas feeds in the potassium hydroxide solution, needing the time more than three days could react the potassium formiate that generates trace under the condition of pressure-fired, does not obviously have industrial production and is worth.That is to say at carbon monoxide and potassium hydroxide more than the normal pressure, under the suitable temperature and just can react the generation potassium formiate.But for industrial production, should take all factors into consideration reaction pressure in conjunction with the type of carbon monoxide gas gas compressor, reaction pressure of the present invention is chosen to be 1.7Mpa-4.0Mpa.
In conjunction with above-mentioned potassium formiate preparation method, the present invention also utilizes air-flow crystallisation by cooling technology to provide a kind of product granularity adjustable granulating equipment.
Granulating equipment of the present invention comprises cylindrical shell, material inlet, adsorber, the annular gas jet pipe, extractor fan, material vibrator, the pressure worm conveyor, temperature-detecting device, at the cylindrical shell top is material inlet, cylindrical shell middle and lower part inwall is fixed with the annular gas jet pipe, the annular gas jet pipe is communicated with the outer adsorber of cylindrical shell, below the annular gas jet pipe, be provided with material vibrator, a pressure worm conveyor is connected in the cylindrical shell bottom of material vibrator below, the pressure worm conveyor the other end is connected products export, be connected to temperature-detecting device above cylindrical shell, cylindrical shell top one side opening connects extractor fan by siphunculus.
Above-mentioned cylindrical shell adopts isodiametric structure formation, and cylinder inboard wall is antiseptic, routinely technology brushing protective system or inside lining anti-corrosive material.
In the cylindrical shell of above-mentioned material inlet below fog-spray nozzle is housed.
Above-mentioned material inlet place can install flowrate control valve additional.
Be evenly distributed with row's spray orifice on the tube wall up of above-mentioned annular gas jet pipe.
On the vent-pipe between above-mentioned extractor fan and the cylindrical shell, also be provided with sack cleaner.
Material vibrator can be fixed in the end in cylinder inboard wall or the cylindrical shell.
The equipment material that contacts with material in the equipment all will adopt corrosion-resistant, resistant to elevated temperatures stainless steel.
The working process of this equipment is as follows:
Liquid to be crystallized (as potassium formiate liquid) material is entered in the cylindrical shell by material inlet, enter the intravital annular gas jet pipe of tube owing to there is the external air of the application cylinder of powerful air exhausting device to purify by adsorber, upwards ejection, meet and the crystallization that is cooled with from top to down mist liquid material in the cylindrical shell, fall on the vibrator after the material crystallization, vibrator makes product enter the pressure worm conveyor smoothly, enters packaging system by material outlet again, can prevent that solid accumulation is in cylindrical shell.In order to improve the product yield, granulating equipment of the present invention also is provided with sack cleaner on the air draft circuit, collects the material particles of being taken out of cylindrical shell by wind by sack cleaner, can be used for the utilization again of product.By controlling the granularity size that mass flow can be regulated crystallized stock.
Equipment of the present invention can be applied to other cleaning, good fluidity, the not granulation of easily-crystallized stock equally.
The present invention compared with prior art has following excellent results:
1. production process route of the present invention is simple, the novel uniqueness of production unit, building-up reactions product are single, the potassium formiate content of product up to more than 97%, product is spherical particle, and controllable granularity, can satisfy the specification of quality of external client fully, especially can satisfy the demand of China's oil drilling well industry high quality potassium formiate product to this product.Adopt the technology of the present invention, successive is produced high-quality potassium formiate product on a large scale, and production cost is all lower than the cost of domestic existing hydrochlorate method, sodium formate method explained hereafter potassium formiate product, and the existing market does not have similar granular product sale.The saturated potassium formiate solution product fluid density that the present invention produces reaches 1.58g/cm
3, the content of potassium formiate solid crystal product just can reach more than 97% very like a cork, and is practical.And the purity of domestic existing potassium formiate solid crystal product has only about 95%.
2. the invention solves the difficulty of spherical potassium formiate granulation, the potassium formiate product appearance of utilizing the granulating equipment of air-flow crystallisation by cooling technological invention to make is good, and the granularity of product is adjustable, and the value-added content of product height is firmly got external client's favorable comment.Solved the big difficult problem of potassium formiate marumerizer technical difficulty, greatly improved the class of potassium formiate product, and product granularity adjustable, satisfied the requirement of external client to potassium formiate shape of product and granularity, value-added content of product height.The selling price of product is higher about 50 yuan than flaked product, and easily by external client's approval, increases the ability of the foreign exchange earning of this product.
3. the present invention adopts process for cleanly preparing, and whole process of production does not have any three waste discharge, and the production operation environment is clean and tidy, safety.Product of the present invention if can large-scale application in the drilling well industry, except meeting improves drilling quality, improves drilling speed, also can well protect the oil field surrounding enviroment, can not cause soil salinization, obvious social benefit.
(4) description of drawings
Fig. 1 is an example structure synoptic diagram of granulating equipment of the present invention.
Fig. 2 is the synoptic diagram of annular gas jet pipe.
Wherein, 1, cylindrical shell, 2, material inlet, 3, floating dust adsorption unit, 4, the annular gas jet pipe, 5, extractor fan, 6, sack cleaner, 7, material vibrator, 8, the pressure worm conveyor, 9, temperature-detecting device, 10, products export, 11, shower nozzle, 12, siphunculus, 13, control valve, 14, spray orifice.
(5) embodiment
Embodiment 1:
Carbon monoxide gas concentration: purifying back content is 93%;
The potassium hydroxide product that potassium hydroxide solution adopts ionic membrane method to produce, concentration is weight percentage 25%;
2: 1 CO (carbon monoxide converter) gas of mol ratio is fed in the potassium hydroxide solution, and building-up reactions is 4 hours under 225 ℃ of temperature, pressure 2.3Mpa condition, makes potassium formiate product dilute solution.Above-mentioned potassium formiate product dilute solution is evaporated to 180 ℃ of normal pressures saturated, the potassium formiate liquid product.Above-mentioned potassium formiate liquid product is evaporated to molten state for 185 ℃ at normal pressure, at normal pressure, the granulation of air-flow crystallisation by cooling makes spherical shape potassium formiate particulate product 110 ℃ the time.
Embodiment 2:
Carbon monoxide gas concentration: purifying back content is 90%;
The potassium hydroxide product that potassium hydroxide solution adopts ionic membrane method to produce, concentration is weight percentage 20%;
1: 1 CO (carbon monoxide converter) gas of mol ratio is fed in the potassium hydroxide solution, and potassium hydroxide and carbon monoxide mass ratio are 3: 1, and building-up reactions is 3 hours under 200 ℃ of temperature, pressure 3.5Mpa condition, makes potassium formiate product dilute solution.Above-mentioned potassium formiate product dilute solution is evaporated to 185 ℃ of normal pressures saturated, the potassium formiate liquid product.Above-mentioned potassium formiate liquid product is evaporated to molten state for 190 ℃ at normal pressure, at normal pressure, the granulation of air-flow crystallisation by cooling makes spherical shape potassium formiate particulate product 150 ℃ the time.
Embodiment 3:
Carbon monoxide gas concentration: purifying back content is 88%;
The potassium hydroxide product that potassium hydroxide solution adopts ionic membrane method to produce, concentration is weight percentage 20%;
3: 1 CO (carbon monoxide converter) gas of mol ratio is fed in the potassium hydroxide solution, and potassium hydroxide and carbon monoxide mass ratio are 2: 1, and building-up reactions is 5 hours under 210 ℃ of temperature, pressure 2Mpa condition, makes potassium formiate product dilute solution.Above-mentioned potassium formiate product dilute solution is evaporated to 195 ℃ of normal pressures saturated, the potassium formiate liquid product.Above-mentioned potassium formiate liquid product is evaporated to molten state for 200 ℃ at normal pressure, at normal pressure, the granulation of air-flow crystallisation by cooling makes spherical shape potassium formiate particulate product 130 ℃ the time.
Embodiment 4:
The granulating equipment structure is a material inlet 2 at isodiametric cylindrical shell 1 top as shown in Figure 1, in the material inlet 2 below cylindrical shells 1 fog-spray nozzle 11 is housed, and material inlet 1 place installs flowrate control valve 13 additional, to regulate the granularity of crystallized stock.Cylindrical shell 1 middle and lower part inwall is fixed with annular gas jet pipe 3, be evenly distributed with row's spray orifice 14 on the tube wall up of annular gas jet pipe 3, annular gas jet pipe 3 is communicated with the outer adsorber 4 of cylindrical shell, below annular gas jet pipe 3, be provided with material vibrator 7, a worm conveyor 8 is connected in the cylindrical shell bottom of material vibrator 7 belows, worm conveyor 8 the other ends are connected products export, and products export can be connected with product packing unit.Be connected to temperature-detecting device 9 above cylindrical shell 1, cylindrical shell 1 top one side opening connects extractor fan 5 by vent-pipe 12, also is provided with sack cleaner 6 on the vent-pipe 12 between extractor fan 5 and the cylindrical shell.Cylindrical shell 1 inwall brushing protective system.The equipment material that contacts with material in the equipment is and adopts corrosion-resistant, resistant to elevated temperatures stainless steel.Potassium formiate liquid to be crystallized is entered in the cylindrical shell 1 by material inlet 2, cylindrical shell 1 outer air purifies the annular gas jet pipe 4 that enters in the cylindrical shell 1 by adsorber 3, upwards ejection, meet with from top to down mist potassium formiate liquid material in the cylindrical shell and make the potassium formiate crystallisation by cooling, the potassium formiate particle is fallen on the vibrator 7, enter worm conveyor 8 again, collect the material particles of taking cylindrical shell 1 because of wind out of, be used for the utilization again of product by sack cleaner 6.
120 ℃ of the equipment design temperature of present embodiment, the design pressure normal pressure, standard pipe fitting pressure rating is selected the PN1.0 grade for use, and the product granularity scope that makes is the 40-80 order.
Claims (8)
1. the preparation method of a granular potassium formiate is characterized in that, comprises the steps:
(1) with mol ratio (1～3): 1 CO (carbon monoxide converter) gas feeds in the potassium hydroxide solution, 150 ℃～230 ℃, be higher than under 1.7Mpa to the 4.0Mpa condition building-up reactions 1.5～6 hours, make potassium formiate product dilute solution;
(2) saturated with being evaporated under the above-mentioned potassium formiate product dilute solution normal pressure, get the potassium formiate liquid product;
(3) above-mentioned potassium formiate liquid product is evaporated to molten state under 150 ℃～200 ℃, normal pressure, makes granular potassium formiate product in the granulation of 110 ℃～180 ℃ temperature downstream crystallisation by cooling.
2. the preparation method of granular potassium formiate as claimed in claim 1 is characterized in that, described potassium hydroxide solution concentration is at weight percent 5%～35%.
3. granulating equipment, it is characterized in that, at the cylindrical shell top material inlet is arranged, cylindrical shell middle and lower part inwall is fixed with the annular gas jet pipe, and the annular gas jet pipe is communicated with the outer adsorber of cylindrical shell, is provided with material vibrator below the annular gas jet pipe, a pressure worm conveyor is connected in the cylindrical shell bottom of material vibrator below, the pressure worm conveyor the other end is connected products export, is connected to temperature-detecting device on cylindrical shell top, and cylindrical shell top one side opening connects extractor fan by siphunculus.
4. granulating equipment as claimed in claim 3 is characterized in that, described cylindrical shell is an equal diameter structure formation, and cylinder inboard wall is through antiseptic.
5. granulating equipment as claimed in claim 3 is characterized in that, in the cylindrical shell of described material inlet below fog-spray nozzle is housed.
6. granulating equipment as claimed in claim 3 is characterized in that, flowrate control valve is equipped with at described material inlet place.
7. granulating equipment as claimed in claim 3 is characterized in that, is evenly distributed with row's spray orifice on the tube wall up of described annular gas jet pipe.
8. granulating equipment as claimed in claim 3 is characterized in that, is provided with sack cleaner on the vent-pipe between described extractor fan and the cylindrical shell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031390226A CN1193977C (en) | 2003-08-28 | 2003-08-28 | Process for preparing granular patassium formate and its pelletizing equipment |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031390226A CN1193977C (en) | 2003-08-28 | 2003-08-28 | Process for preparing granular patassium formate and its pelletizing equipment |
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| CN1491931A true CN1491931A (en) | 2004-04-28 |
| CN1193977C CN1193977C (en) | 2005-03-23 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104016849A (en) * | 2013-02-28 | 2014-09-03 | 黄冈师范学院 | Co-production process for formic acid and monopotassium phosphate |
| CN105502692A (en) * | 2015-11-30 | 2016-04-20 | 西安建筑科技大学 | Fluidized bed water treatment device realizing chemical crystallization circulating granulation |
| CN110776880A (en) * | 2019-11-15 | 2020-02-11 | 四川正蓉实业有限公司 | Organic salt of aggravation inhibitor for well drilling and completion |
| CN115867513A (en) * | 2020-08-21 | 2023-03-28 | 博特化工装置股份公司 | Device for producing alkali metal hydroxide particles |
-
2003
- 2003-08-28 CN CNB031390226A patent/CN1193977C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104016849A (en) * | 2013-02-28 | 2014-09-03 | 黄冈师范学院 | Co-production process for formic acid and monopotassium phosphate |
| CN105502692A (en) * | 2015-11-30 | 2016-04-20 | 西安建筑科技大学 | Fluidized bed water treatment device realizing chemical crystallization circulating granulation |
| CN105502692B (en) * | 2015-11-30 | 2018-01-12 | 西安建筑科技大学 | A kind of chemicrystallization circulates granulating fluidized bed water treatment facilities |
| CN110776880A (en) * | 2019-11-15 | 2020-02-11 | 四川正蓉实业有限公司 | Organic salt of aggravation inhibitor for well drilling and completion |
| CN115867513A (en) * | 2020-08-21 | 2023-03-28 | 博特化工装置股份公司 | Device for producing alkali metal hydroxide particles |
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| Publication number | Publication date |
|---|---|
| CN1193977C (en) | 2005-03-23 |
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