CN1167663C

CN1167663C - Process for synthesizing potassium formate

Info

Publication number: CN1167663C
Application number: CNB001128140A
Authority: CN
Inventors: 杨显云; 戴祖宏; 姜仁普
Original assignee: Individual
Current assignee: Individual
Priority date: 2000-03-31
Filing date: 2000-03-31
Publication date: 2004-09-22
Anticipated expiration: 2020-03-31
Also published as: CN1273962A

Abstract

The present invention relates to a new technology for synthesizing potassium formate. CO with the preparation purity more than 90% and K(OH) solution with the concentration of 3 to 5M are synthesized into synthesis liquid with the preparation concentration of 370 to 420 g/l in the premises of the working pressure of 1 to 1.7MPa and the synthesis temperature of 180DEGC. The synthesis liquid is settled, is heated to be crystallized or concentrated, and is dried to prepare the product. The prepared product has high quality and low production cost, and the present invention provides wide prospect for the scale industrial production.

Description

The potassium formiate synthesis technique

Technical field

The invention belongs to the formate preparing technical field, be specifically related to technology with the synthetic potassium formiate of carbon monoxide.

Background technology

Industry potassium formiate product has important use in petroleum drilling.Producing the potassium formiate past has two kinds of methods, and the one, adopt acid-base method to produce chemical reagent type potassium formiate, owing to cost an arm and a leg, can not be as suitability for industrialized production.Another kind is to choose with KCL and sulfuric acid reaction, produces K through metathesis ₂SO ₄After again with formic acid reaction and make potassium formiate, this complex process, and will produce a large amount of contaminate environment goods and materials is not so still be the ideal production technique.Japanese documentation JP7714716 " AlkaIi metal Formates " has reported a kind of with basic metal and carbonate and CO ₂Produce NaCOOH and KCOOH with H-H reaction, it is 73.1% HCO that this technology can make concentration ₂Na, and fact proved that this quality product is very inferior, no practical value.

Summary of the invention

The objective of the invention is to deficiency at existing explained hereafter potassium formiate Industrial products, a kind of CO of utilization gas and K (OH) are provided the synthetic novel process that generates potassium formiate, its technology is easy, reach 95% high quality potassium formiate except producing acquisition content, satisfy outside the petroleum drilling fluid needs of China Petroleum, if be used for producing formic acid, its by-product still is the first fertilizer (K that China extremely lacks ₂SO ₄), not only harmless but also very useful.

The present invention adopts CO gas and K (OH) pressurization synthesis method, its processing requirement prepares purity and reaches K (OH) solution that CO gas more than 90% and concentration are 3-5M, in operating pressure is 1000-1700kPa, synthesis temperature is syntheticly under 170 ℃-220 ℃ the prerequisite to produce the synthetic liquid that concentration is 6.6-7.5mol/L, make its crystallization or concentrated by heating after sinking clearly, final drying makes product.

Processing requirement:

1.CO the concentration of gas must reach more than 90% by purifying, and preferably is selected in more than 95% the content requirement O of other gases ₂＜0.15, CO ₂＜0.4%, H ₃S+SO does not have.To the control of CO gas concentration, be for the safety coefficient in the high quality, high yield and the raising production process that guarantee to generate KCOOH.

2.K (OH) preparation of solution: according to the requirement system of the synthetic liquid concentration of required KCOOH, such as, when the synthetic liquid concentration of need KCOOH is 6.073mol/L, the concentration of its preparation K (OH) is 3.8mol/L, high more as required synthetic liquid concentration requirement, then the proportioning of K (OH) is high more, roughly is controlled between the 3-5M or about 4.29mol/L.

3. reaction synthesis temperature: after CO gas enters reactive system, when the temperature of its preheater rises to 130 ℃, begin to inject good K (OH) solution of outfit with proportioning pump, temperature of reaction is risen to about 190 ℃ answer held stationary, thus the accelerated reaction but right temperature raises, but high more when heating up, then molecular balance moves to the direction of heat absorption, even synthetic good KCOOH is transformed to other materials, so temperature should be controlled between 170 ℃-220 ℃, preferably between 180 ℃-200 ℃.

4. operating pressure (synthesis pressure): 1000-1700kPa, preferably be selected between the 1000-1500kPa, if being lower than 1000kPa, synthetic work pressure can't make CO gas and K (OH) produce building-up reactions, that is to say and to generate KCOOH, so synthesis pressure should be higher than 1000kPa, it is controlled at any scope on earth for well, the pressure that should bear according to synthetic tower and the operating pressure of proportioning pump, and the CO gas flow what and decide, device by the existing synthetic NacooH of China is as the criterion, its work synthesis pressure 1000-1700kPa is for well, but can not be lower than 1000kPa.

5. the condensing crystal of product or drying: the KCOOH product removes and is slightly soluble in ethanol, and the solubleness that is insoluble in the ether outside water is high, and the solubleness in 18 ℃ of cold water is 331g/100g water, is 657g/100g water in 90 ℃ water temperature, so be difficult for crystallization and drying.Find during examination is ground that it can not crystallization in the normal temperature cooling, can not be in freezing crystallization down, even just with broadcast crystal seed method, broken follow the example of etc. can not be achieved the goal, very easily moisture absorption then, this process choice the heating evaporation crystallization, temperature is more than 150 ℃.Drying after the crystallization is controlled at 120 ℃, vacuum-packed in the weighing apparatus temperature.But preferably adopt in the high temperature more than 190 ℃ film-making final vacuum packing to obtain the method for product.

6. pack: adopt iron sealing bucket outward, or plastic seal mouth bucket, the interior plastic bag packaging of using is so that store or transportation.

The advantage positively effect of invention or utility model:

Adopt this synthetic technology, can most adopt mature NacooH producing apparatus, have less investment, characteristics such as easy and simple to handle.Adopt present technique manufacture KCOOH or oil KCOOH product on a large scale, more more economical than acid-base method, this production technique is beneficial to the maintenance environment again simultaneously, and contamination-free produces.The KCOOH quality that present technique is made is good, and its fluid density reaches 1.58g/cm ³, dry product can reach between the 90-98%, can only prepare the potassium formiate good product quality of 73.1% and 63% purity than original technology, and is practical.

Remarkable in economical benefits, existing chemical reagent KCOOH adopts acid-base method to make, and its price is more than 10000 yuan/ton, and the quality product that original industrialization technology is produced is inferior, can not satisfy current specification of quality again.And the good product quality that this explained hereafter goes out, production cost is about 3500 yuan/ton, and its sale price (does not contain packing) about 5500 yuan/ton, provide cost savings greatly, has more the market competitiveness.

Embodiment

Potassium formiate synthesis technique step is as follows:

(1) purifies CO gas, its purity is reached more than 90%, preferably reach more than 95%;

(2) choose the K that concentration is 3-5M (OH) solution, produce the synthetic liquid that concentration is 6.6-7.5mol/L with CO gas is synthetic, operating pressure is 1000-1700kpa, is preferably 1000-1500KPa, and synthesis temperature is 170 ℃-220 ℃, is preferably in 180 ℃-200 ℃,

(3) will synthesize the liquid sedimentation;

(4) evaporation concentration is made the KCOOH liquid that requires density;

Or (5) crystallization or film-making be dried to qualified industrial potassium formiate dry product, and Tc should be more than 150 ℃, and the temperature that dry product is produced in film-making preferably is selected in 190 ℃-220 ℃.

Below for adopting the examination and test of products situation of the KCOOH that this technology makes: (because the existing product-free technology national standard of KCOOH, so use the HCOONa product technology national standard similar with it)

Table 1 test basis and result on July 30th, 1999

The product technology standard	Q/CSH·02-91
The product technology standard	Q/CSH·02-91					Index name	Unit	Technical indicator	Detected result	Test method standard
Acceptable end product	Salable product							Technical indicator
Acceptable end product	Salable product	Purity (HcooK) 〉=	％	95	90			96.90
KOH content≤	％	Purity (HcooK) 〉=	％	95	90	0.5		96.90	0.084
KOH content≤	％	K ₃CO ₃Content≤	％	0.5	1.5	0.5		0.067	0.084
Moisture content≤	％	K ₃CO ₃Content≤	％	0.5	1.5	1.00		0.067	0.88
Moisture content≤	％	Sulfide (in S)≤	％	0.04		1.00		0.018	0.88
Kcl	％	Sulfide (in S)≤	％	0.04		2.00		0.018	1.04
Kcl	％	Outward appearance				2.00		White crystal	1.04

Table 2 test basis and result on December 24th, 1999

The product technology standard	Q/CSH·02-91
The product technology standard	Q/CSH·02-91					Index name	Unit	Technical indicator	Detected result	Test method standard
Acceptable end product	Salable product							Technical indicator
Acceptable end product	Salable product	Purity (HcooK) 〉=	％	95	90			94.77
KOH content≤	％	Purity (HcooK) 〉=	％	95	90	0.5		94.77	0.12
KOH content≤	％	K ₂CO ₃Content≤	％	0.5	1.5	0.5		0.058	0.12
Moisture content≤	％	K ₂CO ₃Content≤	％	0.5	1.5	1.00		0.058	0.57
Moisture content≤	％	Sulfide (in S)≤	％	0.04		1.00		0.020	0.57
Kcl≤	％	Sulfide (in S)≤	％	0.04		2.00		0.020	0.77
Kcl≤	％	Outward appearance				2.00		White crystal	0.77

Claims

1. potassium formiate synthesis technique is characterized in that described technology may further comprise the steps:

(1) purifies CO gas, its purity is reached more than 90%;

(2) choose the K that concentration is 3-5M (OH) solution, produce the synthetic liquid that concentration is 6.6-7.5mol/L with CO gas is synthetic, operating pressure is 1000-1700kPa, and synthesis temperature is 170 ℃-220 ℃;

(3) will synthesize the liquid sedimentation;

(4) evaporation concentration is made KCOOH liquid;

Or (5) crystallization or film-making are dried to the potassium formiate dry product.

2. potassium formiate synthesis technique according to claim 1 is characterized in that: in the described step (1), CO gas sweetening purity reaches more than 95%; In the described step (2), the synthetic operating pressure is 1000-1500kPa, and synthesis temperature is controlled at 180 ℃-200 ℃.

3. potassium formiate synthesis technique according to claim 1 and 2 is characterized in that: the temperature that dry product is produced in film-making is selected in 190 ℃-220 ℃.