CN104743518B

CN104743518B - Application method of nucleation agent used for preparing sodium percarbonate

Info

Publication number: CN104743518B
Application number: CN201510029636.3A
Authority: CN
Inventors: 刘林生; 曾道龙; 骆家明
Original assignee: JIANGXI BOHOLY CHEMICAL Co Ltd
Current assignee: JIANGXI BOHOLY CHEMICAL Co Ltd
Priority date: 2015-01-21
Filing date: 2015-01-21
Publication date: 2017-02-22
Anticipated expiration: 2035-01-21
Also published as: CN104743518A

Abstract

The invention relates to a nucleation agent used for preparing a sodium percarbonate product. The nucleation agent used for preparing the sodium percarbonate product is composed of sodium metasilicate pentahydrate, magnesium sulphate heptahydrate, sodium tripolyphosphate, sodium polyacrylate and hydroxyethylidene-1,1-diphosphonic acid. An additional way comprises that the nucleation agent is added in hydrazine hydrate by-product slurry dissolved in mother solution and in hydrogen peroxide solution and one or more than one in the nucleation agent is added in a crystallization reaction process. The obtained sodium percarbonate product has the advantages that active oxygen content is 14.32%, thermal stability is 95.1%, stability is 70.3%, and particles larger than 40 meshes account for 98% of the total particles.

Description

A kind of using method of the crystallization in motion agent preparing SODIUM PERCARBONATE

Technical field

A kind of using method of the crystallization in motion agent preparing SODIUM PERCARBONATE of the present invention, more particularly to one kind washing soda or Crystallization in motion agent used in hydrazine hydrate by-product production SODIUM PERCARBONATE process.

Background technology

SODIUM PERCARBONATE is molecular formula is Na₂CO₃·1.5H₂The sodium carbonate peroxyhydrate of O, industrial conduct washing combination The bleach of thing.SODIUM PERCARBONATE generally adopts hydrogen peroxide and aqueous sodium carbonate reaction preparation, and referred to as wet method crystallizes processing method, instead Crystallization in motion agent and salting-out agents generally to be added, such as Nacl etc., it is ensured that stablizing of product, submits yield, reduces cost to during answering. The selection wherein having crystallization in motion agent species has a great impact to its product quality.

In Chinese invention CN1330561C, add natrium carbonicum calcinatum in water or circulating mother liquor, after emulsifying hydration reaction The aqueous hydrogen peroxide solution of prepared hydrated sodium carbonate suspension and concentration 25% 70% pours reaction into certain speed that adds React in kettle, mol ratio is 1:1.3-1:1.5, crystallization auxiliary selects sodium silicate, organic phospho acid, ethylenediaminetetraacetic acid or its sodium Salt, one or several mixture of polyacrylamide, at 30 DEG C, the crystallization reaction time is 30-50 minute to crystallization temperature, obtains Best result is 14.6 for active o content, and heat stability is 94.4%, and wet stability is 60.2% high-quality SODIUM PERCARBONATE product Product.

Disclose a kind of sodium percarbonate crystal modifying agent in Chinese invention patent CN1331737C, have phosphate, ethylenediamine Tetraacethyl disodium, hydroxy ethylene diphosphonic acid, ethylene diamine tetra methylene phosphonic acid, polyacrylic acid and water composition, obtain active o content For 13.72%, 0.25-1.00mm granule 92.1% SODIUM PERCARBONATE crystal.

But, each crystallization in motion agent role is different, and disposable addition can not make crystallization in motion agent obtain sufficient profit With, and disposably add for a large amount of production, nor leach well.

Content of the invention

The technical problem to be solved is to provide a kind of using method of the crystallization in motion agent preparing SODIUM PERCARBONATE, step Including：

(1) prepare washing soda slurry：It is completely dissolved in mother solution using washing soda crystal, add 0.15%- 1.1% crystallization in motion agent, adds salting-out agents afterwards, makes salt content be 13-19%, makes washing soda slurry；

(2) prepare dioxygen water mixed liquid：14.7g-16.68g is added to help in every kilogram of 27.5%-70% hydrogen peroxide solution Dioxygen water mixed liquid is made in brilliant agent；

(3) prepare reaction bottom liquid：The crystallization in motion agent of 1.1-3% is added while stirring in mother solution；

(4) crystallization reaction：Reaction temperature controls at 24 DEG C -34 DEG C, washing soda slurry and dioxygen water mixed liquid with 3.2:1-4.4:1 volume velocity is added simultaneously to than while stirring react in the liquid of bottom, and crystallization reaction process intermittent adds Crystallization in motion agent, the amount of every 100kg washing soda slurry adds 0.1-0.2kg, finally gives SODIUM PERCARBONATE crystal.

A kind of preferred as the present invention, crystallization in motion agent in step (1) is metasilicate pentahydrate sodium and Magnesium sulfate heptahydrate, step (2) in, crystallization in motion agent is HEDP (hydroxy ethylidene-diphosphate) and PAAS (sodium polyacrylate), and crystallization in motion agent in step (3) is trimerization phosphorus Sour sodium and Magnesium sulfate heptahydrate, crystallization in motion agent in step (4) is sodium tripolyphosphate.

Another kind of preferred as the present invention, step following (1) prepares washing soda slurry：Washing soda is completely molten In mother solution, add 0.15-0.3% metasilicate pentahydrate sodium mixture to be warming up at 26 DEG C -40 DEG C and start to dissolve, add again after filtration Enter a certain amount of salt, make salt content in 13%-19%, then put into the Magnesium sulfate heptahydrate of 0.5-0.8%, mix homogeneously, stand-by.

(2) prepare dioxygen water mixed liquid：Every kilogram of 27.5%-70% hydrogen peroxide solution adds 7.35g-8.34g stabilizer The dispersant PAAS (sodium polyacrylate) of HEDP (hydroxy ethylene diphosphonic acid) and equivalent, mix homogeneously, it is cooled to -5 DEG C -5 DEG C, stand-by.

(3) prepare reaction bottom liquid：Start stirring, rotating speed is 40 turns/min, reactive tank adds mother solution, dissolving accounts for mother solution The sodium tripolyphosphate of the 1.5-1.7% of weight and the Magnesium sulfate heptahydrate of 1.1-1.3%.

(4) crystallization reaction：Reaction temperature controls between 24 DEG C -34 DEG C, and washing soda slurry in step (1) is synchronous Suddenly in (2) dioxygen water mixed liquid with 3.2:1-4.4:1 volume velocity is added to than while stirring in the liquid of reaction bottom and is crystallized Reaction, reaction is often carried out 15 minutes, adds 0.1-0.2kg sodium tripolyphosphate by the amount of every 100kg washing soda slurry, is obtained SODIUM PERCARBONATE crystal.

Using this crystallization in motion agent and its Adding Way, the active o content of the SODIUM PERCARBONATE product obtaining is 14.32, thermally-stabilised Property be 95.1%, wet stability be 70.3%, granules more than 40 mesh accounts for the 98% of total particle number, with respect to each skill of prior art Art index is obtained for lifting, and adds crystallization in motion agent on the premise of ensureing product quality using the method, promotes industry Change a large amount of production.

Specific embodiment

Used in course of reaction, mother solution is by 6-8% sodium carbonate, 0.7-1.2% hydrogen peroxide, 16%-25% salting-out agents, And 70-75% water composition.Following mother solution refers both to this mother solution.In this invention, described salt is salting-out agents, using Nacl, main Composition is wanted to be NaCl.After reaction terminates, SODIUM PERCARBONATE crystal is leached, obtain mother solution by after the liquid standing clarification of reaction bottom, carry out Recycle.

Embodiment 1

Step is as follows：

1. prepare washing soda slurry：32% mother solution and 67.7% washing soda crystal, wherein mother solution 0.15- 0.3% metasilicate pentahydrate sodium mixture is warming up at 26 DEG C -40 DEG C and starts to dissolve, and adds a certain amount of salt, make salt after filtration Content is in 13%-19%, then puts into the Magnesium sulfate heptahydrate of 0.5-0.8%, and mix homogeneously is stand-by.

2. prepare dioxygen water mixed liquid：Every kilogram of 35% hydrogen peroxide solution adds 8g stabilizer HEDP (hydroxy ethylene two Phosphonic acids) and equivalent dispersant PAAS (sodium polyacrylate), mix homogeneously, be cooled to -5 DEG C -5 DEG C, stand-by.

3. prepare reaction bottom liquid：Start stirring, rotating speed is 40 turns/min, reactive tank adds 1L mother solution, dissolving accounts for mother The sodium tripolyphosphate of the 1.5-1.7% of liquid weight and the Magnesium sulfate heptahydrate of 1.1-1.3%.

4. crystallization reaction：Reaction temperature controls between 24 DEG C -34 DEG C, by washing soda slurry in step 1 with step 2 Middle dioxygen water mixed liquid is added simultaneously in the reaction bottom liquid in step 3 with certain speed ratio, and volume velocity is than for 4.4:1, 80 revs/min of speed are stirred simultaneously, and reaction is often carried out 15 minutes, add 6-7g sodium tripolyphosphate, add twice altogether, react into Row 50 minutes, consumes 16.8L washing soda slurry, 4.32L dioxygen water mixed liquid, prepared 5.12kg SODIUM PERCARBONATE crystal.

Table 1 is embodiment of the present invention 2-6, and course of reaction is identical with embodiment, and the selection of just different crystallization in motion agent respectively is made Test.Table 2 is embodiment 1-6 Comparative result table.

Table 1

Table 2

Table 3 is comparative example 7-9 and technology ginseng done by the reactions steps difference to hydrogen peroxide content same as Example 1 Number contrast table.

Table 3

Embodiment	Hydrogen peroxide content	HEDP/PAAS consumption	Dioxygen water consumption	SODIUM PERCARBONATE yield	Active o content (%)
						7	27.5%	7.35g	5.50L	5.01kg	13.97%
8	50%	8.20g	3.03L	5.18kg	14.3%
						9	70%	8.34g	2.16L	5.21kg	14.41%

Embodiment 10

1. prepare washing soda slurry：32% mother solution and 67.7% washing soda, 0.15-0.3% five water is inclined Sodium silicate mixture is warming up to 26 DEG C to start to dissolve, and heats up always until whole dissolve, maximum temperature is less than 40 DEG C, after filtration again Add certain salt, make salt content in 13-19%, then put into the Magnesium sulfate heptahydrate of 0.5-0.8%, mix homogeneously, stand-by.

2. prepare dioxygen water mixed liquid：Every kilogram of 35% hydrogen peroxide adds 8g stabilizer HEDP (hydroxy ethylene diphosphonic acid) With the dispersant PAAS (sodium polyacrylate) of equivalent, mix homogeneously, it is cooled to -5 DEG C -5 DEG C, stand-by.

3. start stirring, frequency is 40 turns/min, 25m³0.55m is added in reactor³Mother solution, dissolving accounts for mother solution weight The sodium tripolyphosphate of 1.5-1.7% and the Magnesium sulfate heptahydrate of 1.1-1.3%.

4. reaction temperature is controlled between 24 DEG C -34 DEG C, by the washing soda having configured slurry and hydrogen peroxide mixing Liquid is with volume velocity than for 3.2:1 is added simultaneously in reactive tank, and after 15 minutes, speed is than improve to 3.7:1, add 5-6kg tri- Polyphosphate sodium, improve mixing speed is 80 turns/min simultaneously, improves volume velocity ratio again for 4.4 after 15 minutes:1, then Secondary addition 5-6kg sodium tripolyphosphate, improves mixing speed to 120 turns/min, consumes 13.76m in 50 minutes³Washing soda Slurry, 3.38m³Dioxygen water mixed liquid, reaction terminates, and after continuing stirring 5-10 minute, rewinding is filtered.Obtain SODIUM PERCARBONATE 4.2 Ton.

Claims

1. a kind of using method of the crystallization in motion agent preparing SODIUM PERCARBONATE it is characterised in that：

(1) prepare washing soda slurry：It is completely dissolved in mother solution using washing soda crystal, add 0.15%-1.1% Crystallization in motion agent, adds salting-out agents afterwards, makes salt content be 13-19%, makes washing soda slurry;

(2) prepare dioxygen water mixed liquid：Add 14.7g-16.68g crystallization in motion agent system in every kilogram of 27.5%-70% hydrogen peroxide solution Become dioxygen water mixed liquid;

(4) crystallization reaction：Reaction temperature controls at 24 DEG C -34 DEG C, and the washing soda having configured slurry and hydrogen peroxide are mixed Close liquid with volume velocity than for 3.2:1 is added simultaneously in reactive tank, and after 15 minutes, speed ratio brings up to 3.7:1, add crystallization in motion Agent, stirring, improved volume velocity ratio for 4.4 after 15 minutes again:1, add crystallization in motion agent, stirring, every 100kg ten aqueous carbonate The amount of sodium slurry adds 0.1-0.2kg, finally gives SODIUM PERCARBONATE crystal.

2. crystallization in motion agent according to claim 1 using method it is characterised in that：Step（1）Middle crystallization in motion agent is that five water are inclined Sodium silicate and Magnesium sulfate heptahydrate, step（2）Middle crystallization in motion agent is HEDP（Hydroxy ethylidene-diphosphate）And PAAS（Sodium polyacrylate）, Step（3）Middle crystallization in motion agent is sodium tripolyphosphate and Magnesium sulfate heptahydrate, step（4）Middle crystallization in motion agent is sodium tripolyphosphate.

3. crystallization in motion agent according to claim 2 using method it is characterised in that：(1) prepare washing soda slurry：Ten Aqueous sodium carbonate is completely dissolved in mother solution, add 0.15-0.3% metasilicate pentahydrate sodium mixture be warming up to start at 26 DEG C -40 DEG C molten Solution, adds a certain amount of salt after filtration, make salt content in 13%-19%, then puts into the Magnesium sulfate heptahydrate of 0.5-0.8%, and mixing is all Even, stand-by；

(2) prepare dioxygen water mixed liquid：Every kilogram of 27.5%-70% hydrogen peroxide solution adds 7.35g-8.34g stabilizer HEDP （Hydroxy ethylene diphosphonic acid）Dispersant PAAS with equivalent（Sodium polyacrylate）, mix homogeneously, it is cooled to -5 DEG C -5 DEG C, treat With；

(3) prepare reaction bottom liquid：Start stirring, rotating speed is 40 turns/min, reactive tank adds mother solution, dissolving accounts for mother solution weight The sodium tripolyphosphate of 1.5-1.7% of amount and the Magnesium sulfate heptahydrate of 1.1-1.3%；

(4) crystallization reaction：Reaction temperature controls between 24 DEG C -34 DEG C, by the same step of washing soda slurry in step (1) (2) in dioxygen water mixed liquid with volume velocity than for 3.2:1 is added simultaneously in reactive tank, and after 15 minutes, speed ratio brings up to 3.7:1, add crystallization in motion agent, stirring, improve volume velocity ratio after 15 minutes again for 4.4:1, add crystallization in motion agent, stir, Add 0.1-0.2kg sodium tripolyphosphate, prepared SODIUM PERCARBONATE crystal by the amount of every 100kg washing soda slurry.