Air-liquid two-phase sulfonation soda pulping process spent lye prepares slurries additive agent
Technical field
The present invention relates to recyclings and field of environment protection field, and in particular to air-liquid two-phase sulfonation soda pulping process
Spent lye prepares slurries additive agent.
Background technology
A kind of novel clean liquid with coal for replacing oil that water-coal-slurry grows up when being oil crisis the 1970s fires
Material.It is by 70% or so coal, 30% or so water and 1% or so additive by certain technological process processing and
At with good mobility and stability, being allowed to atomization by pumping and achieve the effect that stablize burning.So water-coal-slurry
It is a kind of more satisfactory clean fuel, and various boilers can be widely used in as fuel.Water-coal-slurry is in preparation process
Chemical addition agent is added, mainly changes the surface nature of coal grain, can disperse in water, it is good to make coal slurry have
Good mobility and stability.
Phenols wastewater concentration is high, toxicity is big, color and luster is deep, soda acid resiliency is strong, is difficult to biochemical degradation, and product per ton generates about
The waste water of 10-15t causes human body and environment great harm.The waste water treatment is generally acknowledged problem.Its waste component is main
Containing inorganic matters such as a large amount of sodium sulphate, sodium sulfites, and the incomplete organic intermediate products of separation, wherein containing-OH ,-
SO3H isoreactivity groups can not only save the processing cost of waste water, but also can receive apparent economic benefit if can comprehensively utilize.
The first place of China's paper-making industrial waste water discharge capacity and the China COD discharge capacity Jun Ju all types of industries discharge capacity at present.Closely
Nian Lai, country such as continue to increase the dynamics of contamination control and improvement, but are limited to fund, technology and environmental consciousness at many-sided reason,
The enterprise pollution environmental problem of papermaking is not well solved still.The spent lye that pulping by cooking generates during soda pulping process
It is most important pollution sources in paper waste, accounts for about the 90% of entire industrial pollution caused by paper manufacturing, containing a large amount of harmful substance, and its
Containing lignin difficult to degrade and its derivative, it is a kind of overbasic complicated Pollution System, easily causes water pollution and ecology
The serious destruction of environment, belongs to hazardous waste.If these spent lyes cannot be handled effectively and direct emission, not only seriously
Environment is polluted, and the waste of vast resources can be caused.
Invention content
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides air-liquid two-phase sulfonation soda pulping process spent lyes to prepare water-coal-slurry
Additive recycles spent lye, phenols wastewater prepares slurries additive agent, realization recycling and environmental protection.
(2) technical solution
In order to achieve the above object, the present invention is achieved by the following technical programs:
A kind of air-liquid two-phase sulfonation soda pulping process spent lye prepares slurries additive agent, by the raw material of following parts by weight
It is made:80-90 parts of spent lye, 40-48 parts of sulfur dioxide, 65-85 parts of phenols wastewater, 5-9 parts of hydrogen peroxide, 25-45 parts of formaldehyde, liquid
10-20 parts of alkali.
Preferably, it is prepared from the following raw materials in parts by weight:85-90 parts of spent lye, 46-50 parts of sulfur dioxide, phenols are useless
70-80 parts of water, 5-6 parts of hydrogen peroxide, 35-45 parts of formaldehyde, 16-20 parts of liquid caustic soda.
Preferably, it is prepared from the following raw materials in parts by weight:90 parts of spent lye, 48 parts of sulfur dioxide, 75 parts of phenols wastewater,
5.5 parts of hydrogen peroxide, 40 parts of formaldehyde, 18 parts of liquid caustic soda.
Preferably, the preparation method that the air-liquid two-phase sulfonation soda pulping process spent lye prepares slurries additive agent includes
Following steps:
(1) spent lye is added in reaction kettle, is heated to 50-60 DEG C, stirring while is slowly introducing sulfur dioxide, directly
It is finished to being passed through;
(2) phenols wastewater and hydrogen peroxide are added into reaction kettle, is warming up to 70-80 DEG C, it is primary to keep the temperature, continue to reaction kettle
Middle dropwise addition formaldehyde, after being added dropwise, secondary heat preservation adjusts PH to 10 to get product with liquid caustic soda.
Preferably, the time that is passed through of sulfur dioxide described in step (1) is 20-30min.
Preferably, the time for adding of formaldehyde described in step (2) is 20-30min.
Preferably, a soaking time described in step (2) is 1-2h.
Preferably, secondary soaking time described in step (2) is 2-3h
(3) advantageous effect
The present invention provides a kind of air-liquid two-phase sulfonation soda pulping process spent lyes to prepare slurries additive agent, has following
Advantageous effect:
Slurries additive agent prepared by the present invention is not contained only using the spent lye that pulping by cooking during soda pulping process generates
There is its lignin difficult to degrade, also contains the active group hair in the aromatic compounds, with sulfur dioxide, phenols wastewater such as anthraquinone
The reactions such as raw multiple nucleophilic, sulfonation, to enhance product performance.
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
The every other embodiment obtained under the premise of creative work, shall fall within the protection scope of the present invention.
Embodiment 1:
A kind of air-liquid two-phase sulfonation soda pulping process spent lye prepares slurries additive agent, by the raw material of following parts by weight
It is made:85 parts of spent lye, 40 parts of sulfur dioxide, 66 parts of phenols wastewater, 6.5 parts of hydrogen peroxide, 45 parts of formaldehyde, 10 parts of liquid caustic soda.
Above-mentioned air-liquid two-phase sulfonation soda pulping process spent lye prepares the preparation method of slurries additive agent, including following step
Suddenly:
(1) spent lye is added in reaction kettle, is heated to 55 DEG C, stirring while is slowly introducing sulfur dioxide, is passed through
Time is 25min, is finished until being passed through;
(2) phenols wastewater and hydrogen peroxide are added into reaction kettle, is warming up to 75 DEG C, keeps the temperature 1.5h, continues into reaction kettle
Formaldehyde is added dropwise, time for adding 25min after being added dropwise, keeps the temperature 2.5h, and PH to 10 is adjusted to get product with liquid caustic soda.
Embodiment 2:
A kind of air-liquid two-phase sulfonation soda pulping process spent lye prepares slurries additive agent, by the raw material of following parts by weight
It is made:80 parts of spent lye, 45 parts of sulfur dioxide, 85 parts of phenols wastewater, 8.0 parts of hydrogen peroxide, 26 parts of formaldehyde, 12 parts of liquid caustic soda.
Above-mentioned air-liquid two-phase sulfonation soda pulping process spent lye prepares the preparation method of slurries additive agent, including following step
Suddenly:
(1) spent lye is added in reaction kettle, is heated to 50 DEG C, stirring while is slowly introducing sulfur dioxide, is passed through
Time is 20min, is finished until being passed through;
(2) phenols wastewater and hydrogen peroxide are added into reaction kettle, is warming up to 70 DEG C, keeps the temperature 1h, continues to drip into reaction kettle
Add formaldehyde, time for adding 20min after being added dropwise, to keep the temperature 2h, PH to 10 is adjusted to get product with liquid caustic soda.
Embodiment 3:
A kind of air-liquid two-phase sulfonation soda pulping process spent lye prepares slurries additive agent, by the raw material of following parts by weight
It is made:85 parts of spent lye, titanium dioxide S35 part, 80 parts of phenols wastewater, 7.5 parts of hydrogen peroxide, 34 parts of formaldehyde, 15 parts of liquid caustic soda.
Above-mentioned air-liquid two-phase sulfonation soda pulping process spent lye prepares the preparation method of slurries additive agent, including following step
Suddenly:
(1) spent lye is added in reaction kettle, is heated to 60 DEG C, stirring while is slowly introducing sulfur dioxide, is passed through
Time is 30min, is finished until being passed through;
(2) phenols wastewater and hydrogen peroxide are added into reaction kettle, is warming up to 80 DEG C, keeps the temperature 2h, continues to drip into reaction kettle
Add formaldehyde, time for adding 30min after being added dropwise, to keep the temperature 3h, PH to 10 is adjusted to get product with liquid caustic soda.
Embodiment 4:
A kind of air-liquid two-phase sulfonation soda pulping process spent lye prepares slurries additive agent, by the raw material of following parts by weight
It is made:90 parts of spent lye, 48 parts of sulfur dioxide, 75 parts of phenols wastewater, 5.5 parts of hydrogen peroxide, 40 parts of formaldehyde, 18 parts of liquid caustic soda.
Above-mentioned air-liquid two-phase sulfonation soda pulping process spent lye prepares the preparation method of slurries additive agent, including following step
Suddenly:
(1) spent lye is added in reaction kettle, is heated to 55 DEG C, stirring while is slowly introducing sulfur dioxide, is passed through
Time is 28min, is finished until being passed through;
(2) phenols wastewater and hydrogen peroxide are added into reaction kettle, is warming up to 75 DEG C, keeps the temperature 1.3h, continues into reaction kettle
Formaldehyde is added dropwise, time for adding 26min after being added dropwise, keeps the temperature 2.8h, and PH to 10 is adjusted to get product with liquid caustic soda.
Embodiment 5:
A kind of air-liquid two-phase sulfonation soda pulping process spent lye prepares slurries additive agent, by the raw material of following parts by weight
It is made:90 parts of spent lye, 40 parts of sulfur dioxide, 70 parts of phenols wastewater, 8.5 parts of hydrogen peroxide, 34 parts of formaldehyde, 14 parts of liquid caustic soda.
Above-mentioned air-liquid two-phase sulfonation soda pulping process spent lye prepares the preparation method of slurries additive agent, including following step
Suddenly:
(1) spent lye is added in reaction kettle, is heated to 55 DEG C, stirring while is slowly introducing sulfur dioxide, is passed through
Time is 28min, is finished until being passed through;
(2) phenols wastewater and hydrogen peroxide are added into reaction kettle, is warming up to 75 DEG C, keeps the temperature 1.3h, continues into reaction kettle
Formaldehyde is added dropwise, time for adding 26min after being added dropwise, keeps the temperature 2.8h, and PH to 10 is adjusted to get product with liquid caustic soda.
Embodiment 6:
A kind of air-liquid two-phase sulfonation soda pulping process spent lye prepares slurries additive agent, by the raw material of following parts by weight
It is made:86 parts of spent lye, 42 parts of sulfur dioxide, 75 parts of phenols wastewater, 7 parts of hydrogen peroxide, 40 parts of formaldehyde, 12 parts of liquid caustic soda.
Above-mentioned air-liquid two-phase sulfonation soda pulping process spent lye prepares the preparation method of slurries additive agent, including following step
Suddenly:
(1) spent lye is added in reaction kettle, is heated to 53 DEG C, stirring while is slowly introducing sulfur dioxide, is passed through
Time is 25min, is finished until being passed through;
(2) phenols wastewater and hydrogen peroxide are added into reaction kettle, is warming up to 73 DEG C, keeps the temperature 1.5h, continues into reaction kettle
Formaldehyde is added dropwise, time for adding 22min after being added dropwise, keeps the temperature 2.3h, and PH to 10 is adjusted to get product with liquid caustic soda.
Embodiment 7:
A kind of air-liquid two-phase sulfonation soda pulping process spent lye prepares slurries additive agent, by the raw material of following parts by weight
It is made:88 parts of spent lye, 43 parts of sulfur dioxide, 80 parts of phenols wastewater, 8.2 parts of hydrogen peroxide, 28 parts of formaldehyde, 13 parts of liquid caustic soda.
Above-mentioned air-liquid two-phase sulfonation soda pulping process spent lye prepares the preparation method of slurries additive agent, including following step
Suddenly:
(1) spent lye is added in reaction kettle, is heated to 58 DEG C, stirring while is slowly introducing sulfur dioxide, is passed through
Time is 22min, is finished until being passed through;
(2) phenols wastewater and hydrogen peroxide are added into reaction kettle, is warming up to 73 DEG C, keeps the temperature 1.8h, continues into reaction kettle
Formaldehyde is added dropwise, time for adding 24min after being added dropwise, keeps the temperature 2.5h, and PH to 10 is adjusted to get product with liquid caustic soda.
Embodiment 8:
A kind of air-liquid two-phase sulfonation soda pulping process spent lye prepares slurries additive agent, by the raw material of following parts by weight
It is made:88 parts of spent lye, 44 parts of sulfur dioxide, 82 parts of phenols wastewater, 8..3 parts of hydrogen peroxide, 28 parts of formaldehyde, 13 parts of liquid caustic soda.
Above-mentioned air-liquid two-phase sulfonation soda pulping process spent lye prepares the preparation method of slurries additive agent, including following step
Suddenly:
(1) spent lye is added in reaction kettle, is heated to 56 DEG C, stirring while is slowly introducing sulfur dioxide, is passed through
Time is 30min, is finished until being passed through;
(2) phenols wastewater and hydrogen peroxide are added into reaction kettle, is warming up to 79 DEG C, keeps the temperature 1.6h, continues into reaction kettle
Formaldehyde is added dropwise, time for adding 25min after being added dropwise, keeps the temperature 2.5h, and PH to 10 is adjusted to get product with liquid caustic soda.
Selection Xi'an coal green for a long time is research object, and after screening and grading, target slurry concentration is 66%, and additive amount is
The 0.25% of coal butt.Below be product of the present invention behavior pattern compared with other slurries additive agent properties:
As can be seen from the above table, water-coal-slurry made from product of the present invention have high concentration, low-viscosity, good mobility and
Stability, the value with commercial Application, performance are substantially better than other slurries additive agents;Under identical Pulping conditions,
The viscosity of the made slurry of 4 product of embodiment is minimum, and divergence is maximum.
It should be noted that herein, relational terms such as first and second and the like are used merely to a reality
Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation
In any actual relationship or order or sequence.Moreover, the terms "include", "comprise" or its any other variant are intended to
Non-exclusive inclusion, so that the process, method, article or equipment including a series of elements is not only wanted including those
Element, but also include other elements that are not explicitly listed, or further include for this process, method, article or equipment
Intrinsic element.In the absence of more restrictions, the element limited including sentence "including a ...", it is not excluded that
There is also other identical elements in the process, method, article or apparatus that includes the element.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations, although with reference to the foregoing embodiments
Invention is explained in detail, it will be understood by those of ordinary skill in the art that:It still can be to aforementioned each implementation
Technical solution recorded in example is modified or equivalent replacement of some of the technical features;And these modification or
It replaces, the spirit and scope for various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution.