CN107162365A - A kind of preparation method and its application method of deoiling of sludge medicament - Google Patents
A kind of preparation method and its application method of deoiling of sludge medicament Download PDFInfo
- Publication number
- CN107162365A CN107162365A CN201710538805.5A CN201710538805A CN107162365A CN 107162365 A CN107162365 A CN 107162365A CN 201710538805 A CN201710538805 A CN 201710538805A CN 107162365 A CN107162365 A CN 107162365A
- Authority
- CN
- China
- Prior art keywords
- sludge
- deoiling
- apg
- medicament
- retort
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Sludge (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a kind of preparation method of deoiling of sludge medicament in Sludge in Oilfields process field, deoiling of sludge medicament composition and content are：Hydroxymethyl alkyl glucosides is 0.1~1 wt %；Crosslinked fatty alcohol polyoxyethylene blocks polyethers is 0.1~1 wt %；Sodium carbonate is 0.1~5 wt %；Potassium pyrophosphate is 0.01~0.1 wt %；Surplus is water；Hydroxymethyl alkyl glucosides is modified by APG and is made.The invention also discloses a kind of application method of deoiling of sludge medicament, oily sludge is mixed with deoiling of sludge medicament, it is placed in isothermal reaction tank, retort reaction temperature is 200~450 r/min in 45~50 DEG C, stir speed (S.S.), oily sludge is fully washed 1 ~ 2h, and the mixture in retort is stood into 1~3 hour, make mixture shared oil, water, three layers of mud successively from top to bottom, the oil on upper strata is reclaimed, the sludge of lower floor is discharged, the oil in oily sludge is removed.Hydroxymethyl alkyl glucosides of the present invention and other composite reagents, strengthen deoiling effect, and cost is relatively low.
Description
Technical field
The invention belongs to Sludge in Oilfields process field, the preparation method of more particularly to a kind of deoiling of sludge medicament and its
Application method.
Background technology
The petrochemistry industry of China, produces substantial amounts of oily sludge every year, and yield is also rising year by year, oily sludge
As《National Hazard waste register》In polluter, it is necessary to handled, otherwise can be to surrounding enviroment and producing region
Different degrees of influence is produced, and is also a kind of waste to resource, oily composition in recovery sludge is efficiently separated, both can be with
It is also the premise for carrying out oily sludge harmless treatment and recycling to reduce the wasting of resources.
In recent years, domestic and international researcher has carried out substantial amounts of research work to deoiling of sludge, forms many processing sides
Method.In deoiling of sludge field, mainly returned both at home and abroad using quenched separation method, bioremediation, incinerating method, solvent extraction
Oily method and pyrogenic process modification treatment technology are received, but from application effect, there are the following problems：Bioremediation strain is selected
Long, high to the oil content sludge of difficult, process cycle is selected to be difficult in adapt to；Burning method processing cost and operating cost are high, handle
Process can produce the secondary pollutions such as SO2, CO and dust；Solvent extraction absorption method long flow path, complex process, solvent price are high and locate
Reason is costly；Pyrogenic process processing cost of investment height and complex process.
Chemicals treatment is the oily way of recycling of low cost generally acknowledged both at home and abroad, and the exploitation of efficient medicament is key therein,
It is also the practical challenges that current scene carries out deoiling of sludge.In the prior art, using chemicals treatment oily sludge, it is necessary to
Medicament application concentration is higher, and environment temperature also needs control in specified interval, causes cost too high.In Chinese patent database,
Application number 201210023784.0, applying date 2012.02.03 patent of invention discloses a kind of processing of Sludge in Oilfields
Oily sludge also needs press filtration again after preliminary filtering in method, this method, and screen cloth was passed twice through at 90 ~ 120 DEG C, adds
45 ~ 60 DEG C of oil removings are heated to after medicament, are only capable of reclaiming in oily sludge 50% crude oil, the oil removal rate of sludge is low, and step is numerous
Trivial, cost is higher.Application number 201010601322.3, applying date 2010.12.17 patent of invention discloses a kind of containing greasy dirt
Mud thermochemical separating agent and its application method, oily sludge thermochemical separating agent prepared by this method can be used for processing to contain greasy dirt
The processing of mud, particularly sludge from oil tank, can by fill base oil mud residual oil content it is minimum be down to 0.5%, be still unable to reach GB4284 mark
Alignment request be less than 0.3%.
The content of the invention
An object of the present invention is to provide a kind of preparation method of deoiling of sludge medicament, is closed by being modified to APG
Forming surfactants hydroxymethyl alkyl glucosides, hydroxymethyl alkyl glucosides and other composite reagents, strengthen deoiling effect, and compounding is made
Deoiling of sludge medicament oil water interfacial tension it is lower, sludge oil content after processing is less than 0.3%, meets national standard；This dirt
Each composition constituent concentration of Fender oil medicament is lower, the cost needed for the live deoiling of sludge of reduction.
The object of the present invention is achieved like this：A kind of preparation method of deoiling of sludge medicament, the group of deoiling of sludge medicament
Into and content be：Hydroxymethyl alkyl glucosides is 0.1~1 wt %；Crosslinked fatty alcohol polyoxyethylene blocks polyethers is 0.1~1 wt
%；Sodium carbonate is 0.1~5 wt %；Potassium pyrophosphate is 0.01~0.1 wt %；Surplus is water；The deoiling of sludge medicament it is each
Constituent percentage composition sum is percentage hundred；The hydroxymethyl alkyl glucosides is modified by APG and is made.
The present invention is by the modified obtained hydroxymethyl alkyl glucosides of APG, and hydroxymethyl alkyl glucosides is surfactant,
Can further it be dropped with being all that the crosslinked fatty alcohol polyoxyethylene blocks polyethers compounding of surfactant plays additive synergism
Low oil water interfacial tension, improves surfactant and penetrates into Sludge Surface and internal capacity, strengthen sludge dispersion effect, improve
Sludge Surface and internal oily peeling effect, reduction oil and disengage it from shale surface in the surface adhesion force of shale contact surface,
Float and separate, oily sludge is divided into 3 layers of oil, water and sludge, the oil in sludge is more thoroughly separated, after processing
Sludge oil content be less than 0.3%, meet standard GB/T 4284；The concentration of each constituent of this deoiling of sludge medicament is relatively low,
The cost for preparing deoiling of sludge medicament is relatively low, required cost when reducing scene to deoiling of sludge.
As a further improvement on the present invention, the APG is modified as follows：
1）Weak oxide APG：The APG solution for taking mass fraction to be 45 ~ 50% is dissolved in ethanol, APG solution
Be 1 with the volume ratio of ethanol: (1.5 ~ 1.8), stir 5 ~ 15min, add Sarett reagents into above-mentioned solution, APG with
The mass ratio that feeds intake of Sarett reagents is (0.002 ~ 0.004): 1, continue 1 ~ 3h of agitating solution, to APG by weak oxide；
2）Nucleophilic addition：To step 1）Weak oxide product in first add mass fraction be 35 ~ 40% formalin, formaldehyde
The aqueous solution and step 1）In the volume ratio of initial APG solution be (1 ~ 1.33): 1, then be slowly added to concentration into solution and be
The volume ratio of 4 ~ 6% NaOH ethanol solutions, NaOH ethanol solutions and formalin is 1: (1.5 ~ 2), it is heated to reflux, controls
The temperature of mixed solution is sufficiently stirred at 25 ~ 35 DEG C, makes the carbanion PARA FORMALDEHYDE PRILLS(91,95) nucleophilic addition of weak oxide product；
3）Reduction：Sodium borohydride powder is added into step 2）In nucleophilic addition after mixture in, sodium borohydride powder
Addition press step 1）In every 100ml APGs solution for initially choosing add 1.5 ~ 1.8g sodium borohydrides, in ice-water bath
Said mixture is stirred after 3 ~ 5h under cooling condition, aldehyde ketone is reduced to alcohol by sodium borohydride, purify the product of reduction reaction, most
After obtain hydroxymethyl alkyl glucosides.
Sarett reagents are by APG weak oxide, and the APG after weak oxide is with formaldehyde nucleophilic addition, again by boron hydrogen
Change sodium reduction, completion is modified to APG, the step of hydroxymethyl alkyl glucosides, synthesis hydroxymethyl alkyl glucosides is made letter
Single, synthesis cost is relatively low.
As the improvement of the present invention, the reaction that the APG modifying process occurs is：
。
By the basic skills of organic chemistry, synthetic surfactant hydroxymethyl alkyl glucosides, synthetic route is simple, raw material
It is readily available, cost is lower.
As a further improvement on the present invention, the step 1）In APG be made as follows：By grape
Sugar presses 1 with long-chain alkyl alcohol:(1~20) mixed in molar ratio, is heated with stirring to after 45~135 DEG C, adds acidic catalyst and continues
The mol ratio of stirring, glucose and acidic catalyst is 1:(0.1~0.5), glucose carries out acetal dehydration with long-chain alkyl alcohol
Reaction generation APG crude product, unreacted long-chain alkyl alcohol is removed through dealcoholization system, then obtains after decolorization alkyl
Glucosides finished product.Glucose carries out acetal dehydration with long-chain alkyl alcohol and APG is made, and glucose holds with long-chain alkyl alcohol
Easily obtain cost relatively low, the material for having pollution to environment will not be produced during reaction, biotic environment is more friendly.
As the preferred scheme of the present invention, the long-chain alkyl alcohol is hexanol, octanol, nonyl alcohol or decyl alcohol.
As the preferred scheme of the present invention, the acidic catalyst is p-methyl benzenesulfonic acid or benzene sulfonic acid.
As a further improvement on the present invention, the step 3）In by column chromatography or molecular distillation come purifying hydroxymethyl alkane
Base glucosides.
As the preferred scheme of the present invention, the crosslinked fatty alcohol polyoxyethylene blocks polyethers is AEO-7 or peregal.
The second object of the present invention is to provide a kind of application method of the above-mentioned deoiling of sludge medicament prepared, in reaction
Deoiling of sludge medicament and oily sludge are mixed in tank, reaction temperature, stir speed (S.S.) and the reaction time of retort is controlled, it is more thorough
The oil in sludge is removed to bottom, the oil content of the sludge after processing is dropped to less than 0.3%.
The object of the present invention is achieved like this：A kind of application method of deoiling of sludge medicament, comprises the following steps：
By oily sludge and deoiling of sludge medicament according to mass ratio 1:(2~4) mix, be placed in isothermal reaction tank, reaction is set
Tank reaction temperature is 200~450 r/min in 45~50 DEG C, stir speed (S.S.), oily sludge is fully washed 1 ~ 2h, by retort
In mixture stand 1~3 hour, make mixture shared oil, water, three layers of mud successively from top to bottom, pass through retort top
Drainage trough reclaims the oil on upper strata, and the discharge pipeline of retort bottom discharges the sludge of lower floor, removes the oil in oily sludge.
The present invention by deoiling of sludge medicament washed in retort after oily sludge, standing oily sludge from top to bottom according to
Secondary shared oil, water, three layers of mud, reclaim the oil on upper strata by the drainage trough on retort top, oil can be reused, save money
Source, the discharge pipeline of retort bottom discharges the sludge of lower floor；After deoiling of sludge medicament is mixed with oily sludge, in oily sludge
It has been mixed into water, oily sludge comprising oil, water and mud three-phase, hydroxymethyl alkyl glucosides is surfactant, can be with being all table
The crosslinked fatty alcohol polyoxyethylene blocks polyethers compounding of face activating agent plays additive synergism, further reduction oil-water interfaces
Power, improves surfactant and penetrates into Sludge Surface and internal capacity, strengthen sludge dispersion effect, improves Sludge Surface and interior
Portion's oil peeling effect, the oily surface adhesion force in shale contact surface of reduction, and shale surface is disengaged it from, separation of floating, most
Oily sludge is set to be divided into 3 layers of oil, water and sludge eventually, the oil in sludge is more thoroughly separated, the sludge oil-containing after processing
Amount is less than 0.3%, meets standard GB/T 4284；The concentration of each constituent of this deoiling of sludge medicament is relatively low, prepares sludge and removes
The cost of oily medicament is relatively low, required cost when reducing scene to deoiling of sludge.
As a further improvement on the present invention, the oily sludge is mixed as follows with deoiling of sludge medicament：
1) the oily sludge quality for treating oil removing is m1, is 1 according to the mass ratio of oily sludge and deoiling of sludge medicament:(2~4),
The quality for calculating the deoiling of sludge medicament for needing to prepare is m2, according to each composition and content of deoiling of sludge medicament, with getting ready
Hydroxymethyl alkyl glucosides, crosslinked fatty alcohol polyoxyethylene blocks polyethers, sodium carbonate, potassium pyrophosphate and the water of phase application amount；
2）Step 1 is first added into retort）In with the water got ready, sequentially add step 1）The sodium carbonate of middle half consumption and
Whole potassium pyrophosphates, then add the oily sludge for treating oil removing into retort, and the solidliquid mixture added in retort is stirred
Mix well mixed；
3）Continue to sequentially add step 1 into retort）In with hydroxymethyl alkyl glucosides, the crosslinked fatty alcohol polyoxyethylene got ready
Block polyether and remaining sodium carbonate, oily sludge is uniformly mixed with deoiling of sludge medicament.
When mixing sludge oil removing medicament and oily sludge, whole potassium pyrophosphates and half consumption are first added into retort
Sodium carbonate, then puts into pending oily sludge in retort, finally again successively by hydroxymethyl alkyl glucosides, crosslinked fatty
Alcohol polyoxyethylene blocks polyethers and remaining sodium carbonate are put into retort；, can be with by the way that sodium carbonate is added in two steps
So that oily sludge is more fully washed, deoiling effect improves 10%, and the sludge oil content after scrubbed processing is less than
0.3%, meet standard GB/T 4284.
Brief description of the drawings
The nucleus magnetic hydrogen spectrum figure for the hydroxymethyl alkyl glucosides that Fig. 1 synthesizes for the present invention.
Embodiment
Embodiment 1
The preparation method of the deoiling of sludge medicament of the present embodiment, the composition and content of deoiling of sludge medicament are：Hydroxymethyl alkyl sugar
Glycosides is 0.1 wt %；AEO-7 is 0.1 wt %；Sodium carbonate is 1 wt %；Potassium pyrophosphate is 0.05 wt %；Surplus is water；It is described
Each constituent percentage composition sum of deoiling of sludge medicament is percentage hundred；The hydroxymethyl alkyl glucosides is changed by APG
Property be made.The APG is modified as follows：
1）Weak oxide APG：Take mass fraction be 48.5% APG solution be dissolved in ethanol, APG solution with
The volume ratio of ethanol is 1: 1.66, stirs 10min, and Sarett reagents are added into above-mentioned solution, and APG is tried with Sarett
The mass ratio that feeds intake of agent is 0.003: 1, continues agitating solution 2h, to APG by weak oxide；The APG passes through such as
Lower step is made：Glucose and hexanol are pressed 1:10 mixed in molar ratio, are heated with stirring to after 90 DEG C, add p-methyl benzenesulfonic acid and continue
The mol ratio of stirring, glucose and p-methyl benzenesulfonic acid is 1: 0.3, and glucose carries out acetal dehydration generation alkyl sugar with hexanol
Glycosides crude product, unreacted hexanol is removed through dealcoholization system, then obtains after decolorization APG finished product；
2）Nucleophilic addition：To step 1）Weak oxide product in first add the formalin that mass fraction is 37%, formaldehyde is water-soluble
Liquid and step 1）In the volume ratio of initial APG solution be 1.16: 1, then be slowly added into solution the NaOH that concentration is 5%
The volume ratio of ethanol solution, NaOH ethanol solutions and formalin is 1: 1.75, is heated to reflux, and controls the temperature of mixed solution
At 30 DEG C, and it is sufficiently stirred for, makes the carbanion PARA FORMALDEHYDE PRILLS(91,95) nucleophilic addition of weak oxide product；
3）Reduction：Sodium borohydride powder is added into step 2）In nucleophilic addition after mixture in, sodium borohydride powder
Addition press step 1）In every 100ml APGs solution for initially choosing add 1.66g sodium borohydrides, in ice-water bath cooling
Under the conditions of said mixture is stirred after 4h, aldehyde ketone is reduced to alcohol by sodium borohydride, and column chromatography purifies the product of reduction reaction, most
After obtain hydroxymethyl alkyl glucosides.
The reaction that the APG modifying process occurs is：
。
Using the method for the present embodiment deoiling of sludge chemicals treatment oily sludge, comprise the following steps：From oil field sludge
Oil-containing 10.0wt%, aqueous 80wt%, the oily sludge of the 10wt% containing mud in mummifying pool, by oily sludge and deoiling of sludge medicament
According to mass ratio 1:2 mixing, are placed in isothermal reaction tank, the oily sludge is mixed as follows with deoiling of sludge medicament
Close：
1) the oily sludge quality for treating oil removing is m1, it is 1 according to the mass ratio of oily sludge and deoiling of sludge medicament:2, calculate
The quality for needing the deoiling of sludge medicament prepared is m2=2 m1, according to each composition and content of deoiling of sludge medicament, with getting phase ready
Hydroxymethyl alkyl glucosides, AEO-7, sodium carbonate, potassium pyrophosphate and the water of application amount；
2）Step 1 is first added into retort）In with the water got ready, sequentially add step 1）The sodium carbonate of middle half consumption and
Whole potassium pyrophosphates, then add the oily sludge for treating oil removing into retort, and the solidliquid mixture added in retort is stirred
Mix well mixed；
3）Continue to sequentially add step 1 into retort）In with hydroxymethyl alkyl glucosides, AEO-7 and the remaining carbon got ready
Sour sodium, oily sludge is uniformly mixed with deoiling of sludge medicament.
It is 200 r/min in 50 DEG C, stir speed (S.S.) to set retort reaction temperature, oily sludge is fully washed 1.5h,
Mixture in retort is stood 1 hour, makes mixture shared oil, water, three layers of mud successively from top to bottom, passes through retort
The drainage trough on top reclaims the oil on upper strata, and the discharge pipeline of retort bottom discharges the sludge of lower floor, the lower floor after test oil removing
The oil content of sludge is 0.21%.
Embodiment 2
The preparation method of the deoiling of sludge medicament of the present embodiment, the composition and content of deoiling of sludge medicament are：Hydroxymethyl alkyl sugar
Glycosides is 0.2 wt %；It is average to add as 0.2 wt %；Sodium carbonate is 2 wt %；Potassium pyrophosphate is 0.01wt %；Surplus is water；It is described
Each constituent percentage composition sum of deoiling of sludge medicament is percentage hundred；The hydroxymethyl alkyl glucosides is changed by APG
Property be made.The APG is modified as follows：
1）Weak oxide APG：The APG solution for taking mass fraction to be 45% is dissolved in ethanol, APG solution and second
The volume ratio of alcohol is 1: 1.5, stirs 5min, and Sarett reagents, APG and Sarett reagents are added into above-mentioned solution
The mass ratio that feeds intake is 0.002: 1, continues agitating solution 1h, to APG by weak oxide；The APG by walking as follows
It is rapid to be made：Glucose and octanol are pressed 1:1 mixed in molar ratio, is heated with stirring to after 90 DEG C, adds benzene sulfonic acid and continues to stir, grape
The mol ratio of sugar and benzene sulfonic acid is 1: 0.1, and glucose carries out acetal dehydration generation APG crude product with octanol, through dealcoholysis
System removes unreacted octanol, then obtains after decolorization APG finished product；
2）Nucleophilic addition：To step 1）Weak oxide product in first add the formalin that mass fraction is 35%, formaldehyde is water-soluble
Liquid and step 1）In the volume ratio of initial APG solution be 1: 1, then be slowly added into solution the NaOH second that concentration is 4%
The volume ratio of alcoholic solution, NaOH ethanol solutions and formalin is 1: 1.5, is heated to reflux, and the temperature of control mixed solution exists
25 DEG C, and be sufficiently stirred for, make the carbanion PARA FORMALDEHYDE PRILLS(91,95) nucleophilic addition of weak oxide product；
3）Reduction：Sodium borohydride powder is added into step 2）In nucleophilic addition after mixture in, sodium borohydride powder
Addition press step 1）In every 100ml APGs solution for initially choosing add 1.5g sodium borohydrides, in ice-water bath cooling
Under the conditions of said mixture is stirred after 3h, aldehyde ketone is reduced to alcohol by sodium borohydride, and molecular distillation purifies the product of reduction reaction,
Finally obtain hydroxymethyl alkyl glucosides.
The reaction that the APG modifying process occurs is：
。
Using the method for the present embodiment deoiling of sludge chemicals treatment oily sludge, comprise the following steps：From oil field sludge
Oil-containing 20.0wt%, aqueous 65wt%, the oily sludge of the 15wt% containing mud in mummifying pool, by oily sludge and deoiling of sludge medicament
According to mass ratio 1:3 mixing, are placed in isothermal reaction tank, the oily sludge is mixed as follows with deoiling of sludge medicament
Close：
1) the oily sludge quality for treating oil removing is m1, it is 1 according to the mass ratio of oily sludge and deoiling of sludge medicament:3, calculate
The quality for needing the deoiling of sludge medicament prepared is m2=3 m1, according to each composition and content of deoiling of sludge medicament, with getting phase ready
Hydroxymethyl alkyl glucosides, peregal, sodium carbonate, potassium pyrophosphate and the water of application amount；
2）Step 1 is first added into retort）In with the water got ready, sequentially add step 1）The sodium carbonate of middle half consumption and
Whole potassium pyrophosphates, then add the oily sludge for treating oil removing into retort, and the solidliquid mixture added in retort is stirred
Mix well mixed；
3）Continue to sequentially add step 1 into retort）In with hydroxymethyl alkyl glucosides, peregal and the remaining carbon got ready
Sour sodium, oily sludge is uniformly mixed with deoiling of sludge medicament.
It is 320r/min in 45 DEG C, stir speed (S.S.) to set retort reaction temperature, oily sludge is fully washed 1h, will be anti-
Answer mixture in tank to stand 2 hours, make mixture shared oil, water, three layers of mud successively from top to bottom, pass through retort top
Drainage trough reclaim the oil on upper strata, the discharge pipeline of retort bottom discharges the sludge of lower floor, lower floor's sludge after test oil removing
Oil content be 0.28%.
Embodiment 3
The preparation method of the deoiling of sludge medicament of the present embodiment, the composition and content of deoiling of sludge medicament are：Hydroxymethyl alkyl sugar
Glycosides is 0.5 wt %；It is average to add as 0.3 wt %；Sodium carbonate is 5 wt %；Potassium pyrophosphate is 0.1wt %；Surplus is water；It is described
Each constituent percentage composition sum of deoiling of sludge medicament is percentage hundred；The hydroxymethyl alkyl glucosides is changed by APG
Property be made.The APG is modified as follows：
1）Weak oxide APG：The APG solution for taking mass fraction to be 50% is dissolved in ethanol, APG solution and second
The volume ratio of alcohol is 1: 1.8, stirs 15min, and Sarett reagents, APG and Sarett reagents are added into above-mentioned solution
The mass ratio that feeds intake is 0.004: 1, continues agitating solution 3h, to APG by weak oxide；The APG by walking as follows
It is rapid to be made：Glucose and nonyl alcohol are pressed 1:20 mixed in molar ratio, are heated with stirring to after 135 DEG C, add benzene sulfonic acid and continue to stir, Portugal
The mol ratio of grape sugar and benzene sulfonic acid is 1: 0.5, and glucose carries out acetal dehydration generation APG crude product with nonyl alcohol, through de-
Alcohol system removes unreacted nonyl alcohol, then obtains after decolorization APG finished product；
2）Nucleophilic addition：To step 1）Weak oxide product in first add the formalin that mass fraction is 40%, formaldehyde is water-soluble
Liquid and step 1）In the volume ratio of initial APG solution be 1.33: 1, then be slowly added into solution the NaOH that concentration is 6%
The volume ratio of ethanol solution, NaOH ethanol solutions and formalin is 1: 2, is heated to reflux, and the temperature of control mixed solution exists
35 DEG C, and be sufficiently stirred for, make the carbanion PARA FORMALDEHYDE PRILLS(91,95) nucleophilic addition of weak oxide product；
3）Reduction：Sodium borohydride powder is added into step 2）In nucleophilic addition after mixture in, sodium borohydride powder
Addition press step 1）In every 100ml APGs solution for initially choosing add 1.8g sodium borohydrides, in ice-water bath cooling
Under the conditions of said mixture is stirred after 5h, aldehyde ketone is reduced to alcohol by sodium borohydride, and molecular distillation purifies the product of reduction reaction,
Finally obtain hydroxymethyl alkyl glucosides.
The reaction that the APG modifying process occurs is：
。
Using the method for the deoiling of sludge chemicals treatment oily sludge of the present embodiment, comprise the following steps：It is dirty from oil field
Oil-containing 40wt%, aqueous 22wt%, the oily sludge of the 38wt% containing mud in mud mummifying pool, by oily sludge and deoiling of sludge medicament
According to mass ratio 1:4 mixing, are placed in isothermal reaction tank, the oily sludge is mixed as follows with deoiling of sludge medicament
Close：
1) the oily sludge quality for treating oil removing is m1, it is 1 according to the mass ratio of oily sludge and deoiling of sludge medicament:4, calculate
The quality for needing the deoiling of sludge medicament prepared is m2= 4m1, according to each composition and content of deoiling of sludge medicament, with getting phase ready
Hydroxymethyl alkyl glucosides, peregal, sodium carbonate, potassium pyrophosphate and the water of application amount；
2）Step 1 is first added into retort）In with the water got ready, sequentially add step 1）The sodium carbonate of middle half consumption and
Whole potassium pyrophosphates, then add the oily sludge for treating oil removing into retort, and the solidliquid mixture added in retort is stirred
Mix well mixed；
3）Continue to sequentially add step 1 into retort）In with hydroxymethyl alkyl glucosides, peregal and the remaining carbon got ready
Sour sodium, oily sludge is uniformly mixed with deoiling of sludge medicament.
It is 450r/min in 47 DEG C, stir speed (S.S.) to set retort reaction temperature, oily sludge is fully washed 2h, will be anti-
Answer mixture in tank to stand 3 hours, make mixture shared oil, water, three layers of mud successively from top to bottom, pass through retort top
Drainage trough reclaim the oil on upper strata, the discharge pipeline of retort bottom discharges the sludge of lower floor, lower floor's sludge after test oil removing
Oil content be 0.25%.
Embodiment 4
The preparation method of the deoiling of sludge medicament of the present embodiment, the composition and content of deoiling of sludge medicament are：Hydroxymethyl alkyl sugar
Glycosides is 1 wt %；AEO-7 is 1 wt %；Sodium carbonate is 0.1 wt %；Potassium pyrophosphate is 0.06wt %；Surplus is water；The dirt
Each constituent percentage composition sum of Fender oil medicament is percentage hundred；The hydroxymethyl alkyl glucosides is modified by APG
It is made.The APG is modified as follows：
1）Weak oxide APG：Take mass fraction be 48.5% APG solution be dissolved in ethanol, APG solution with
The volume ratio of ethanol is 1: 1.66, stirs 10min, and Sarett reagents are added into above-mentioned solution, and APG is tried with Sarett
The mass ratio that feeds intake of agent is 0.003: 1, continues agitating solution 2h, to APG by weak oxide；The APG passes through such as
Lower step is made：Glucose and certain herbaceous plants with big flowers alcohol are pressed 1:10 mixed in molar ratio, are heated with stirring to after 90 DEG C, add p-methyl benzenesulfonic acid and continue
The mol ratio of stirring, glucose and p-methyl benzenesulfonic acid is 1: 0.3, and glucose carries out acetal dehydration generation alkyl sugar with certain herbaceous plants with big flowers alcohol
Glycosides crude product, unreacted certain herbaceous plants with big flowers alcohol is removed through dealcoholization system, then obtains after decolorization APG finished product；
2）Nucleophilic addition：To step 1）Weak oxide product in first add the formalin that mass fraction is 37%, formaldehyde is water-soluble
Liquid and step 1）In the volume ratio of initial APG solution be 1.2: 1, then be slowly added into solution the NaOH that concentration is 5%
The volume ratio of ethanol solution, NaOH ethanol solutions and formalin is 1: 2, is heated to reflux, and the temperature of control mixed solution exists
30 DEG C, and be sufficiently stirred for, make the carbanion PARA FORMALDEHYDE PRILLS(91,95) nucleophilic addition of weak oxide product；
3）Sodium borohydride powder is added into step 2）In nucleophilic addition after mixture in, the addition of sodium borohydride powder
Amount presses step 1）In every 100ml APGs solution for initially choosing add 1.53g sodium borohydrides, under ice-water bath cooling condition
After said mixture stirring 5h, aldehyde ketone is reduced to alcohol by sodium borohydride, and column chromatography purifies the product of reduction reaction, finally obtained
Hydroxymethyl alkyl glucosides.
The reaction that the APG modifying process occurs is：
。
Using the method for the deoiling of sludge chemicals treatment oily sludge of the present embodiment, comprise the following steps：It is dirty from oil field
Oil-containing 57wt%, aqueous 20wt%, the oily sludge of the 23wt% containing mud in mud mummifying pool, by oily sludge and deoiling of sludge medicament
According to mass ratio 1:4 mixing, are placed in isothermal reaction tank, the oily sludge is mixed as follows with deoiling of sludge medicament
Close：
1) the oily sludge quality for treating oil removing is m1, it is 1 according to the mass ratio of oily sludge and deoiling of sludge medicament:4, calculate
The quality for needing the deoiling of sludge medicament prepared is m2=4 m1, according to each composition and content of deoiling of sludge medicament, with getting phase ready
Hydroxymethyl alkyl glucosides, AEO-7, sodium carbonate, potassium pyrophosphate and the water of application amount；
2）Step 1 is first added into retort）In with the water got ready, sequentially add step 1）The sodium carbonate of middle half consumption and
Whole potassium pyrophosphates, then add the oily sludge for treating oil removing into retort, and the solidliquid mixture added in retort is stirred
Mix well mixed；
3）Continue to sequentially add step 1 into retort）In with hydroxymethyl alkyl glucosides, AEO-7 and the remaining carbon got ready
Sour sodium, oily sludge is uniformly mixed with deoiling of sludge medicament.
It is 400r/min in 45 DEG C, stir speed (S.S.) to set retort reaction temperature, oily sludge is fully washed 2h, will be anti-
Answer mixture in tank to stand 3 hours, make mixture shared oil, water, three layers of mud successively from top to bottom, pass through retort top
Drainage trough reclaim the oil on upper strata, the discharge pipeline of retort bottom discharges the sludge of lower floor, lower floor's sludge after test oil removing
Oil content be 0.05%.
Keep the content point of crosslinked fatty alcohol polyoxyethylene blocks polyethers, sodium carbonate and potassium pyrophosphate in deoiling of sludge medicament
Not Wei 1 wt %, 5 wt % and 0.1 wt % it is constant, configure the deoiling of sludge medicament of different hydroxymethyl alkyl glycoside concentrations, processing
Oily content is that 57 wt %, the content of shale are 43 wt % in the live oily sludge of certain oil field sludge mummifying pool, sludge, dirty
The mass ratio of Fender oil medicament and oily sludge is 4:1, result is as shown in the table.
Learnt by form, the deoiling of sludge medicament deoiling effect after addition hydroxymethyl alkyl glucosides is further strengthened, oil removing
Oil content is less than 0.3% in sludge afterwards；With the concentration increase of hydroxymethyl alkyl glucosides, the deoiling effect of deoiling of sludge medicament
Become more preferable, oil content is lower in the sludge after oil removing；Can be more thorough by the oil in oily sludge by hydroxymethyl alkyl glucosides
Separate to bottom.
The invention is not limited in above-described embodiment, on the basis of technical scheme disclosed by the invention, the skill of this area
Art personnel are according to disclosed technology contents, it is not necessary to which performing creative labour just can make one to some of which technical characteristic
A little to replace and deform, these are replaced and deformed within the scope of the present invention.
Claims (10)
1. a kind of preparation method of deoiling of sludge medicament, it is characterised in that the composition and content of deoiling of sludge medicament be：Methylol
APG is 0.1~1 wt %；Crosslinked fatty alcohol polyoxyethylene blocks polyethers is 0.1~1 wt %；Sodium carbonate is 0.1~5
wt %；Potassium pyrophosphate is 0.01~0.1 wt %；Surplus is water；Each constituent percentage composition of the deoiling of sludge medicament it
With for percentage hundred；The hydroxymethyl alkyl glucosides is modified by APG and is made.
2. the preparation method of a kind of deoiling of sludge medicament according to claim 1, it is characterised in that the APG leads to
Following steps are crossed to be modified：
1）Weak oxide APG：The APG solution for taking mass fraction to be 45 ~ 50% is dissolved in ethanol, APG solution
Be 1 with the volume ratio of ethanol: (1.5 ~ 1.8), stir 5 ~ 15min, add Sarett reagents into above-mentioned solution, APG with
The mass ratio that feeds intake of Sarett reagents is (0.002 ~ 0.004): 1, continue 1 ~ 3h of agitating solution, to APG by weak oxide；
2）Nucleophilic addition：To step 1）Weak oxide product in first add mass fraction be 35 ~ 40% formalin, formaldehyde
The aqueous solution and step 1）In the volume ratio of initial APG solution be (1 ~ 1.33): 1, then be slowly added to concentration into solution and be
The volume ratio of 4 ~ 6% NaOH ethanol solutions, NaOH ethanol solutions and formalin is 1: (1.5 ~ 2), it is heated to reflux, controls
The temperature of mixed solution is sufficiently stirred at 25 ~ 35 DEG C, makes the carbanion PARA FORMALDEHYDE PRILLS(91,95) nucleophilic addition of weak oxide product；
3）Reduction：Sodium borohydride powder is added into step 2）In nucleophilic addition after mixture in, sodium borohydride powder
Addition press step 1）In every 100ml APGs solution for initially choosing add 1.5 ~ 1.8g sodium borohydrides, in ice-water bath
Said mixture is stirred after 3 ~ 5h under cooling condition, aldehyde ketone is reduced to alcohol by sodium borohydride, purify the product of reduction reaction, most
After obtain hydroxymethyl alkyl glucosides.
3. the preparation method of a kind of deoiling of sludge medicament according to claim 2, it is characterised in that the APG changes
Property process occur reaction be：
。
4. a kind of preparation method of deoiling of sludge medicament according to claim 2, it is characterised in that the step 1）In
APG is made as follows：Glucose and long-chain alkyl alcohol are pressed 1:(1~20) mixed in molar ratio, is heated with stirring to
After 45~135 DEG C, add acidic catalyst and continue to stir, the mol ratio of glucose and acidic catalyst is 1:(0.1~0.5),
Glucose carries out acetal dehydration generation APG crude product with long-chain alkyl alcohol, and unreacted long-chain is removed through dealcoholization system
Alkylol, then obtain after decolorization APG finished product.
5. a kind of preparation method of deoiling of sludge medicament according to claim 4, it is characterised in that the long-chain alkyl alcohol
For hexanol, octanol, nonyl alcohol or decyl alcohol.
6. a kind of preparation method of deoiling of sludge medicament according to claim 4, it is characterised in that the acidic catalyst
For p-methyl benzenesulfonic acid or benzene sulfonic acid.
7. a kind of preparation method of deoiling of sludge medicament according to claim 2, it is characterised in that the step 3）In lead to
Cross column chromatography or molecular distillation carrys out purifying hydroxymethyl APG.
8. a kind of preparation method of deoiling of sludge medicament according to claim 1, it is characterised in that the crosslinked fatty alcohol
Polyoxyethylene blocks polyethers is AEO-7 or peregal.
9. the application method of a kind of deoiling of sludge medicament according to claim 1, it is characterised in that comprise the following steps：
By oily sludge and deoiling of sludge medicament according to mass ratio 1:(2~4) mix, be placed in isothermal reaction tank, reaction is set
Tank reaction temperature is 200~450 r/min in 45~50 DEG C, stir speed (S.S.), oily sludge is fully washed 1 ~ 2h, by retort
In mixture stand 1~3 hour, make mixture shared oil, water, three layers of mud successively from top to bottom, pass through retort top
Drainage trough reclaims the oil on upper strata, and the discharge pipeline of retort bottom discharges the sludge of lower floor, removes the oil in oily sludge.
10. a kind of application method of deoiling of sludge medicament according to claim 9, it is characterised in that the oily sludge
Mixed as follows with deoiling of sludge medicament：
1) the oily sludge quality for treating oil removing is m1, it is 1 according to the mass ratio of oily sludge and deoiling of sludge medicament:(2~4), meter
The quality for calculating the deoiling of sludge medicament for needing to prepare is m2, according to each composition and content of deoiling of sludge medicament, with getting phase ready
Hydroxymethyl alkyl glucosides, crosslinked fatty alcohol polyoxyethylene blocks polyethers, sodium carbonate, potassium pyrophosphate and the water of application amount；
2）Step 1 is first added into retort）In with the water got ready, sequentially add step 1）The sodium carbonate of middle half consumption and
Whole potassium pyrophosphates, then add the oily sludge for treating oil removing into retort, and the solidliquid mixture added in retort is stirred
Mix well mixed；
3）Continue to sequentially add step 1 into retort）In with hydroxymethyl alkyl glucosides, the crosslinked fatty alcohol polyoxyethylene got ready
Block polyether and remaining sodium carbonate, oily sludge is uniformly mixed with deoiling of sludge medicament.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710538805.5A CN107162365B (en) | 2017-07-04 | 2017-07-04 | Preparation method and use method of sludge oil removal agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710538805.5A CN107162365B (en) | 2017-07-04 | 2017-07-04 | Preparation method and use method of sludge oil removal agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107162365A true CN107162365A (en) | 2017-09-15 |
| CN107162365B CN107162365B (en) | 2020-07-07 |
Family
ID=59822606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710538805.5A Active CN107162365B (en) | 2017-07-04 | 2017-07-04 | Preparation method and use method of sludge oil removal agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107162365B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110241304A (en) * | 2019-06-26 | 2019-09-17 | 中国科学院过程工程研究所 | A method of cutting oily iron mud regeneration |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5006239A (en) * | 1986-11-20 | 1991-04-09 | Tetra Technologies, Inc. | apparatus for treatment of oily sludge |
| WO1996003412A1 (en) * | 1994-07-22 | 1996-02-08 | Henkel Corporation | Process for making alkyl polyglycosides |
| JP4167919B2 (en) * | 2003-03-27 | 2008-10-22 | ハイモ株式会社 | Sludge dewatering method |
| CN104342327A (en) * | 2013-08-08 | 2015-02-11 | 厦门泰益新洁净科技有限公司 | Oil-stain cleaning agent as well as preparation method and use method thereof |
| CN104710089A (en) * | 2015-03-23 | 2015-06-17 | 东营金岛环境工程有限公司 | Oily sludge dehydration technology |
| CN105418697A (en) * | 2015-11-02 | 2016-03-23 | 中国石油天然气股份有限公司 | Alkyl glycoside sulfonate surfactant and preparation method and application thereof |
-
2017
- 2017-07-04 CN CN201710538805.5A patent/CN107162365B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5006239A (en) * | 1986-11-20 | 1991-04-09 | Tetra Technologies, Inc. | apparatus for treatment of oily sludge |
| WO1996003412A1 (en) * | 1994-07-22 | 1996-02-08 | Henkel Corporation | Process for making alkyl polyglycosides |
| JP4167919B2 (en) * | 2003-03-27 | 2008-10-22 | ハイモ株式会社 | Sludge dewatering method |
| CN104342327A (en) * | 2013-08-08 | 2015-02-11 | 厦门泰益新洁净科技有限公司 | Oil-stain cleaning agent as well as preparation method and use method thereof |
| CN104710089A (en) * | 2015-03-23 | 2015-06-17 | 东营金岛环境工程有限公司 | Oily sludge dehydration technology |
| CN105418697A (en) * | 2015-11-02 | 2016-03-23 | 中国石油天然气股份有限公司 | Alkyl glycoside sulfonate surfactant and preparation method and application thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110241304A (en) * | 2019-06-26 | 2019-09-17 | 中国科学院过程工程研究所 | A method of cutting oily iron mud regeneration |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107162365B (en) | 2020-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101357903B (en) | Novel technique for preparing 4-formyl amino antipyrine | |
| CN106278827A (en) | A kind of method and device of extract and separate phenolic compound from coal derived oils | |
| CN104276926B (en) | By drippolene C8The discoloration method of the crude styrene that fraction extracting rectifying obtains | |
| CN103145286A (en) | Pre-treatment method of high-concentration wastewater | |
| CN105176565B (en) | A kind of method that heterogeneous reaction separates tar sand oil | |
| CN101875853B (en) | Non-hydrofining method for coker gas oil | |
| CN106590719A (en) | Oil sand asphalt solvent extraction separation system and process | |
| CN112675574A (en) | Method for extracting and separating phenolic components in phenol oil by using hydroxyl functionalized ionic liquid with double hydrogen bond sites | |
| CN109825322B (en) | Method for extracting phenolic substances from coal tar or direct coal liquefaction oil | |
| CN107162365A (en) | A kind of preparation method and its application method of deoiling of sludge medicament | |
| CN100391918C (en) | Method of separating wool acid and lanonol from wool grease | |
| CN100347273C (en) | Complex extracting and dephenolizing method for alkaline slag of smeltery | |
| CN102241580A (en) | Method for recovering organic carboxylic acids from corn chemical alcohol reaction kettle residues by utilizing complex extraction | |
| CN106955680A (en) | One kind oil refining spent bleaching clay continuous regeneration method | |
| CN104845662A (en) | A method for extracting phenolic compounds in coal liquefaction oil | |
| CN102992951B (en) | Method for preparing high-purity refined methanol by three-tower rectification | |
| CN102115224B (en) | Method for pretreating production waste water of fenoxaprop pesticide | |
| CN110407686A (en) | A method of the separating naphthenic acid from mixing organic matter | |
| CN105084634A (en) | Pretreatment method of rubber ingredient production wastewater | |
| CN100572309C (en) | A kind of oil-bearing sludge decomposition method | |
| CN1294087C (en) | Method for treating waste acid from refining benzene for coking plant | |
| CN106315891B (en) | Dephenolizing method and dephenolizing device for phenol-containing wastewater generated in phenol refining | |
| CN107937020A (en) | A kind of efficient breaking method of the two-step method of lipopeptid | |
| CN101768510B (en) | Method for improving trans-cinnamic aldehyde content in cassia oil | |
| CN105296134B (en) | The regeneration method of used oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |