CN105800733A - Inorganic and organic compound demulsifying agent and preparation and application method thereof - Google Patents

Inorganic and organic compound demulsifying agent and preparation and application method thereof Download PDF

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CN105800733A
CN105800733A CN201610161119.6A CN201610161119A CN105800733A CN 105800733 A CN105800733 A CN 105800733A CN 201610161119 A CN201610161119 A CN 201610161119A CN 105800733 A CN105800733 A CN 105800733A
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inorganic
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propylene glycol
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CN105800733B (en
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李孟
陈琪
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Wuhan University of Technology WUT
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

The invention relates to the technical field of oil-containing wastewater treatment, in particular to an inorganic and organic compound demulsifying agent and a preparation method thereof. The inorganic and organic compound demulsifying agent is prepared from polyaluminum ferric silicate and propylene glycol polyether. Polyaluminum ferric silicate and propylene glycol polyether are mixed under the stirring condition to generate the polyaluminum ferric silicate and propylene glycol polyether demulsifying agent. The use quantity of the demulsifying agent is small, the use range is wide, the effect is good, dehydration speed is high, and the demulsifying agent has the low-temperature demulsifying effect.

Description

A kind of inorganic-organic hybrid type demulsifier and preparation, application process
Technical field
The present invention relates to oiliness sewage treatment technical field, be specifically related to inorganic-organic hybrid type demulsifier and preparation thereof, answer Use method.
Background technology
Oily waste water mainly includes the waste water of oil field waste, oil plant and petrochemical plant, and in waste water, oil pollution material is except weight Jiao The relative density of oil is outside more than 1.1, and remaining relative density is both less than 1.In sewage, general oil content is at 1-20%, moisture content At 80-99%, oily waste water can settle in process facility and pipe-line equipment together with particle in waste water and iron scale, Form being normally carried out of the greasy filth group with bigger stickiness, blocking pipeline and equipment impact production；Oily waste water enters water body, meeting Forming oil film on the water surface, can hinder water reoxygenation effect, reduce due to dissolved oxygen in water body, algae photosynthesis is limited System, affects hydrobiological normal growth, makes aquatic animals and plants have oily taste or toxicity, even make water body foul, and destroys water resource Value；Oils is attached on the fish gill, and fish can be made to suffocate, and when concentration is 200mg/L, Fish can not survive；It is attached on On algae, plankton, them can be made dead；Oils can suppress aquatic bird lay eggs and hatch, and makes birds mortality time serious； Use oily waste water irrigated farmland, oil point and derivant thereof by mulching soil and the surface of plant, the hole of blocking soil, stop sky Gas penetrates, and makes soil and microorganism can not be normally carried out metabolism, makes agricultural product quality and practical value decline, meeting time serious Causing crop production reduction or death, oils migrates downward in soil, it is also possible to cause serious underground water pollution.According to statistics, Containing crude oil and the most about 300,000 tons of goods thereof in the waste water that oil field, the whole world, oil plant and petrochemical plant are discharged every year.Containing greasy dirt Containing cacodorous noxious substances such as substantial amounts of benzene homologues, phenols, anthracene, pyrenes in water, if not being acted upon directly discharging, can be right Surrounding soil, water body, air pollute, in sewage possibly together with substantial amounts of pathogen, parasite (ovum), copper, zinc, The heavy metal such as chromium, hydrargyrum, the poisonous and harmful substance of the difficult degradations such as salt and Polychlorinated biphenyls, dioxin, radionuclide.
Along with improving constantly of people's living standard and becoming increasingly abundant of material life, people's living standard creates big leap, People are more and more higher to environmental requirement, the safe and healthy problem becoming people's critical concern.The heaviest to environment of China Depending on, wastewater discharge standard petroleum-type < 10mg/l, phenyl amines < 2mg/l.At present, main Petroleum & Petrochemical Enterprises oily waste water inside and outside the province The problem that existing demulsifier is the most inefficient, water quality treatment oil content is higher of utilization is there is in water in processing.
Summary of the invention
The technical problem to be solved is the deficiency existed for above-mentioned prior art and provides a kind of inorganic-organic hybrid Type demulsifier and preparation, application process, this demulsifier consumption is few, range width, effective, rate of water loss soon and have low Temperature demulsification.
The present invention solves that the technical scheme that problem set forth above is used is:
A kind of inorganic-organic hybrid type demulsifier, comprises poly-ferro-silico aluminium and propylene glycol polyethers, described poly-ferro-silico aluminium and propylene glycol poly- The mass ratio of ether is (49～54): 100.
By such scheme, the chemical expression of described poly-ferro-silico aluminium can be FemAln(SiO3)x, wherein n/m is 0.5～2, and 3 (n+m)-2x=0.Described poly-ferro-silico aluminium uses poly-ferro-silico aluminium solution, and poly-ferro-silico aluminium solution manufacturing method can be: according to poly-silicon The chemical expression Fe of ferro-aluminummAln(SiO3)xMiddle element of Fe, the mol ratio of Al, Si, weigh iron chloride, aluminum sulfate and modification and live SiClx acid, then adds aluminum sulfate and iron chloride under conditions of stirring by modified active silicic acid, after stirring, aging prepared Poly-ferro-silico aluminium solution, the effective solid content of the most poly-ferro-silico aluminium is 5-10%.Wherein, mixing speed is 60～100rad/min, stirs Mix 30～60min, the most aging 1～2h.
By such scheme, the preparation method of described modified active silicic acid is: waterglass is 1:(7～10 with the ratio of water quality), will Waterglass is dissolved in water, obtains waterglass diluent；Waterglass diluent is joined in sulfuric acid solution, after high degree of agitation has been reacted After standing, obtain modified active silicic acid.Wherein, sulfuric acid solution pH is 0.1～1, waterglass diluent and sulfuric acid solution volume Ratio is 1:(1.5～2)；The speed of high degree of agitation is 80～120rad/min, and stirring, 10～15min, stands after reaction completely 30min～1h.
By such scheme, the preparation method of described propylene glycol polyethers is: with propylene glycol for initiator and expoxy propane and oxirane Hybrid reaction in high pressure, prepares 110～140 DEG C of reactions.Wherein, the mass ratio of propylene glycol, expoxy propane and oxirane For 1:(300～400): (200～240), this propylene glycol polyethers is the water-soluble demulsifier with propylene glycol as initiator, average molecular matter Amount is linear expoxy propane, the ethylene oxide block copolyether of 2000～5000, the mass ratio of ethylene oxide block be 10%～ 40%.
The preparation method of above-mentioned inorganic-organic hybrid type demulsifier is: stirred at normal temperatures with polyethers demulsifier by poly-ferro-silico aluminium Mixing, i.e. obtains inorganic-organic hybrid type demulsifier.
The preparation method of above-mentioned inorganic-organic hybrid type demulsifier, more specifically step is: by proportioning, by propylene glycol polyethers It is dissolved in solvent, under 70～80 DEG C of temperature, drips poly-ferro-silico aluminium solution, after stirring is completely dissolved to it, obtain inorganic-organic hybrid Type demulsifier.Wherein, solvent accounts for the mass percent of inorganic-organic hybrid type demulsifier is 30-50%；Solvent can use water Or mass fraction 3～7% methanol aqueous solution；Rate of addition is 1～100ml/s, and mixing speed is 10～240rad/min.
Inorganic-organic hybrid type demulsifier of the present invention may be used for oily waste water, including oil field waste, oil plant and oil The waste water etc. in chemical plant, the demulsifier solution that said method is configured and wastewater volume are than for 1:10, generally at 10～50 DEG C Lower stirring is reacted.In oily waste water, general oil content is 1～20%, moisture content 80～99%, pH=6.2～7.5, wherein Oil pollution material is in addition to more than 1.1 except the relative density of tar heavy oil, and remaining relative density is both less than 1.
Compared with prior art, the invention has the beneficial effects as follows:
First, the present invention selects poly-ferro-silico aluminium and propylene glycol polyethers to react, and has synthesized the novel breakdown of emulsion of inorganic-organic hybrid Agent, consumption is few, range width, effective, rate of water loss soon and have low-temperature demulsification effect.
Second, the present invention places stable performance for a long time, not only has adsorption bridging and electrical neutralization, Er Qieneng Give full play to aluminum, ferric flocculant advantage, combine polysilicon acid bonding assemble, adsorption bridging usefulness and aluminum salt flocculant flco Greatly, the features such as good decoloring performance, Ferric Salt Flocculants flco are closely knit, sedimentation velocity is fast；It is provided simultaneously with propylene glycol polyethers breakdown of emulsion Agent dewatering speed is fast, and the oil content of wastewater of abjection is low, and oil-water interfaces are clear, the feature that water colour is good.
Accompanying drawing explanation
Fig. 1 is the structural representation of inorganic-organic hybrid type demulsifier of the present invention.
Detailed description of the invention
In order to be more fully understood that the present invention, it is further elucidated with present disclosure below in conjunction with embodiment, but the present invention not only office It is limited to the following examples.
Embodiment 1
A kind of inorganic-organic hybrid type demulsifier, the mass ratio of the most poly-ferro-silico aluminium and propylene glycol polyethers is (49～54): 100.
A kind of inorganic-organic hybrid type demulsifier, its preparation method comprises the steps:
(1) preparation of modified active silicic acid: weigh 90g waterglass and add 500ml water and dissolve under agitation, obtaining water glass Glass weak solution；Measure 1+5 sulphuric acid (1 volume concentrated sulphuric acid+5 volume distilled water shakes up) 1000ml, water glass solution is joined sulfur In acid solution, simultaneously with the speed high degree of agitation of 120rad/min；After standing 30min after having reacted, obtain activated silicic acid.One Formula three parts.
(2) preparation of poly-ferro-silico aluminium:
A, measure the activated silicic acid of 500ml, under conditions of 60rad/min stirs, add aluminum sulfate and the 18g iron chloride of 38g, Stop stirring after 30min, after aging 1h, prepare liquid poly-ferro-silico aluminium A sample, wherein molal quantity (Al3++Fe3+):SiO3 2- =2:3, Al3+: Fe3+=2:1；
B, measure the activated silicic acid of 500ml, under conditions of 80rad/min stirs, add aluminum sulfate and the 27g iron chloride of 28.5g, Stop stirring after 30min, after aging 1h, prepare liquid poly-ferro-silico aluminium B sample, wherein molal quantity (Al3++Fe3+):SiO3 2- =2:3, Al3+: Fe3+=1:1；
C, measure the activated silicic acid of 500ml, under conditions of 100rad/min stirs, add aluminum sulfate and the 36g iron chloride of 19g, Stop stirring after 30min, after aging 1h, prepare liquid poly-ferro-silico aluminium C sample, wherein molal quantity (Al3++Fe3+):SiO3 2- =2:3, Al3+: Fe3+=1:2.
(3) preparation of propylene glycol polyether demulsification agent: propylene glycol 2g and catalyst potassium hydroxide are put in autoclave, uses Air in nitrogen displacement still, under stir speed (S.S.), 60rad/min is warming up to 130 DEG C, adds ring continuously at below pressure 0.3MPa Ethylene Oxide, until 800g, adds oxirane until 480g, continues reaction 2h, lower the temperature and still, obtain propylene glycol polyethers breakdown of emulsion Agent.
(4) preparation of inorganic-organic hybrid type demulsifier:
A, at normal temperatures take 100g propylene glycol polyether demulsification agent be dissolved in 500ml, 5% methanol solution in, keep 80 DEG C of perseverances of solution Temperature, is slowly added dropwise A sample poly-ferro-silico aluminium solution 500ml (poly-ferro-silico aluminium solution 642g, the most poly-ferro-silico aluminium with 1ml/s 49.72g), and stir 240rad/min, after it is completely dissolved, just obtains poly-ferro-silico aluminium A-propylene glycol polyethers compound demulsifying Agent.
B, at normal temperatures take 100g propylene glycol polyether demulsification agent be dissolved in 500ml, 5% methanol solution in, keep 80 DEG C of perseverances of solution Temperature, is slowly added dropwise B sample poly-ferro-silico aluminium solution 500ml (poly-ferro-silico aluminium solution 641.5g, the most poly-ferro-silico aluminium with 1ml/s 49.72g), and stir 240rad/min, after it is completely dissolved, just obtains poly-ferro-silico aluminium B-propylene glycol polyethers compound demulsifying Agent.
C, at normal temperatures take 100g propylene glycol polyether demulsification agent be dissolved in 500ml, 5% methanol solution in, keep 80 DEG C of perseverances of solution Temperature, is slowly added dropwise C sample poly-ferro-silico aluminium solution 500ml (poly-ferro-silico aluminium solution 641g, the most poly-ferro-silico aluminium with 1ml/s 53.02g), and stir 240rad/min, after it is completely dissolved, just obtains poly-ferro-silico aluminium C-propylene glycol polyethers compound demulsifying Agent.
Stable performance placed for a long time by above-mentioned gained demulsifier.In 100mL Hubei Zhong Bi environmental protection Science and Technology Co., Ltd. The oily waste water that thered is provided (in oily waste water, oil content is 1～20%, moisture content 80～99%, pH=6.2～7.5, wherein oil Pollutant matter is in addition to more than 1.1 except the relative density of tar heavy oil, and remaining relative density is both less than 1) in add above-mentioned three kinds respectively Demulsifier 10ml, and respectively at 10 DEG C, 25 DEG C, stir 30rad/min at a temperature of 50 DEG C, after reaction 2h, record dehydration rate, As shown in table 1.
Table 1
Embodiment 2
A kind of inorganic-organic hybrid type demulsifier, the mass ratio of the most poly-ferro-silico aluminium and propylene glycol polyethers is 50:100.
A kind of inorganic-organic hybrid type demulsifier, its preparation method comprises the steps:
(1) preparation of activated silicic acid: weigh 90g waterglass and add 500ml water and dissolve under agitation, obtaining waterglass dilute Solution.Measure 1+5 sulphuric acid (1 volume concentrated sulphuric acid+5 volume distilled water shakes up) 1000ml, water glass solution is joined sulphuric acid In solution, simultaneously with the speed high degree of agitation of 80rad/min.Just activated silicic acid is obtained after standing 1h after having reacted.In triplicate.
(2) preparation of poly-ferro-silico aluminium:
A, measure the activated silicic acid of 500ml, under conditions of 60rad/min stirs, add aluminum sulfate and the 18g iron chloride of 38g, Stop stirring after 30min, after aging 2h, prepare liquid poly-ferro-silico aluminium A sample, wherein molal quantity (Al3++Fe3+):SiO3 2- =2:3, Al3+: Fe3+=2:1；
B, measure the activated silicic acid of 500ml, under conditions of 80rad/min stirs, add aluminum sulfate and the 18g iron chloride of 38g, Stop stirring after 45min, after aging 2h, prepare liquid poly-ferro-silico aluminium B sample, wherein molal quantity (Al3++Fe3+):SiO3 2- =2:3, Al3+: Fe3+=2:1；
C, measure the activated silicic acid of 500ml, under conditions of 100rad/min stirs, add aluminum sulfate and the 18g iron chloride of 38g, Stop stirring after 60min, after aging 2h, prepare liquid poly-ferro-silico aluminium C sample, wherein molal quantity (Al3++Fe3+):SiO3 2- =2:3, Al3+: Fe3+=2:1；
(3) preparation of propylene glycol polyether demulsification agent monomer: propylene glycol 2g and catalyst potassium hydroxide are put into autoclave In, with the air in nitrogen displacement still, under stir speed (S.S.), 60rad/min is warming up to 130 DEG C, continuous at below pressure 0.3MPa Add expoxy propane until 800g, add oxirane until 480g, continue reaction 2h, lower the temperature and still, obtain propylene glycol polyethers Demulsifier.
(4) preparation of inorganic-organic hybrid type demulsifier:
A, at normal temperatures take 100g propylene glycol polyether demulsification agent be dissolved in 500ml, 5% methanol solution in, keep 80 DEG C of perseverances of solution Temperature, is slowly added dropwise A sample poly-ferro-silico aluminium solution 500ml (poly-ferro-silico aluminium solution 642g, the most poly-ferro-silico aluminium with 1ml/s 49.72g), and stir 240rad/min, after it is completely dissolved, just obtains poly-ferro-silico aluminium A-propylene glycol polyethers compound demulsifying Agent.
B, at normal temperatures take 100g propylene glycol polyether demulsification agent be dissolved in 500ml, 5% methanol solution in, keep 80 DEG C of perseverances of solution Temperature, is slowly added dropwise B sample poly-ferro-silico aluminium solution 500ml (poly-ferro-silico aluminium solution 642g, the most poly-ferro-silico aluminium with 1ml/s 49.72g), and stir 240rad/min, after it is completely dissolved, just obtains poly-ferro-silico aluminium B-propylene glycol polyethers compound demulsifying Agent.
C, at normal temperatures take 100g propylene glycol polyether demulsification agent be dissolved in 500ml, 5% methanol solution in, keep 80 DEG C of perseverances of solution Temperature, is slowly added dropwise C sample poly-ferro-silico aluminium solution 500ml (poly-ferro-silico aluminium solution 642g, the most poly-ferro-silico aluminium with 1ml/s 49.72g), and stir 240rad/min, after it is completely dissolved, just obtains poly-ferro-silico aluminium C-propylene glycol polyethers compound demulsifying Agent.
Stable performance placed for a long time by above-mentioned gained demulsifier.In 100mL Hubei Zhong Bi environmental protection Science and Technology Co., Ltd. The oily waste water that thered is provided (in oily waste water, oil content is 1～20%, moisture content 80～99%, pH=6.2～7.5, wherein oil Pollutant matter is in addition to more than 1.1 except the relative density of tar heavy oil, and remaining relative density is both less than 1) in add above-mentioned three kinds respectively Demulsifier 10ml, and respectively at 10 DEG C, 25 DEG C, stir 30rad/min at a temperature of 50 DEG C, after reaction 2h, record dehydration rate, As shown in table 2.
Table 2
Embodiment 3
A kind of inorganic-organic hybrid type demulsifier, the mass ratio of the most poly-ferro-silico aluminium and propylene glycol polyethers is 50:100.
A kind of inorganic-organic hybrid type demulsifier, its preparation method comprises the steps:
(1) preparation of activated silicic acid: weigh 90g waterglass and add 500ml water and dissolve under agitation, obtaining waterglass dilute Solution.Measure 1+5 sulphuric acid (1 volume concentrated sulphuric acid+5 volume distilled water shakes up) 1000ml, water glass solution is joined sulphuric acid In solution, simultaneously with the speed high degree of agitation of 120rad/min.Just activated silicic acid is obtained after standing 30min after having reacted.One formula Three parts.
(2) preparation of poly-ferro-silico aluminium:
A, measure the activated silicic acid of 500ml, under conditions of 60rad/min stirs, add aluminum sulfate and the 18g iron chloride of 38g, Stop stirring after 30min, after aging 2h, prepare liquid poly-ferro-silico aluminium A sample, wherein molal quantity (Al3++Fe3+):SiO3 2- =2:3, Al3+: Fe3+=2:1；
B, measure the activated silicic acid of 500ml, under conditions of 80rad/min stirs, add aluminum sulfate and the 18g iron chloride of 38g, Stop stirring after 45min, after aging 2h, prepare liquid poly-ferro-silico aluminium B sample, wherein molal quantity (Al3++Fe3+):SiO3 2- =2:3, Al3+: Fe3+=2:1；
C, measure the activated silicic acid of 500ml, under conditions of 100rad/min stirs, add aluminum sulfate and the 18g iron chloride of 38g, Stop stirring after 60min, after aging 2h, prepare liquid poly-ferro-silico aluminium C sample, wherein molal quantity (Al3++Fe3+):SiO3 2- =2:3, Al3+: Fe3+=2:1；
(3) preparation of propylene glycol polyether demulsification agent: propylene glycol 2g and catalyst potassium hydroxide are put in autoclave, uses Air in nitrogen displacement still, under stir speed (S.S.), 60rad/min is warming up to 130 DEG C, adds ring continuously at below pressure 0.3MPa Ethylene Oxide, until 800g, adds oxirane until 480g, continues reaction 2h, lower the temperature and still, obtain propylene glycol polyethers breakdown of emulsion Agent.
(4) preparation of inorganic-organic hybrid type demulsifier:
A, at normal temperatures take 100g propylene glycol polyether demulsification agent be dissolved in 500ml, 5% methanol solution in, keep 80 DEG C of perseverances of solution Temperature, is slowly added dropwise A sample poly-ferro-silico aluminium solution 500ml (poly-ferro-silico aluminium solution 642g, the most poly-ferro-silico aluminium with 1ml/s 49.72g), and stir 240rad/min, after it is completely dissolved, just obtains poly-ferro-silico aluminium A-propylene glycol polyethers compound demulsifying Agent.
B, at normal temperatures take 100g propylene glycol polyether demulsification agent be dissolved in 500ml, 5% methanol solution in, keep 80 DEG C of perseverances of solution Temperature, is slowly added dropwise B sample poly-ferro-silico aluminium solution 500ml (poly-ferro-silico aluminium solution 642g, the most poly-ferro-silico aluminium with 1ml/s 49.72g), and stir 100rad/min, after it is completely dissolved, just obtains poly-ferro-silico aluminium B-propylene glycol polyethers compound demulsifying Agent.
C, at normal temperatures take 100g propylene glycol polyether demulsification agent be dissolved in 500ml, 5% methanol solution in, keep 80 DEG C of perseverances of solution Temperature, is slowly added dropwise C sample poly-ferro-silico aluminium solution 500ml (poly-ferro-silico aluminium solution 642g, the most poly-ferro-silico aluminium with 1ml/s 49.72g), and stir 10rad/min, after it is completely dissolved, just obtains poly-ferro-silico aluminium C-propylene glycol polyethers composite demulsifying agent.
Stable performance placed for a long time by above-mentioned gained demulsifier.In 100mL Hubei Zhong Bi environmental protection Science and Technology Co., Ltd. The oily waste water that thered is provided (in oily waste water, oil content is 1～20%, moisture content 80～99%, pH=6.2～7.5, wherein oil Pollutant matter is in addition to more than 1.1 except the relative density of tar heavy oil, and remaining relative density is both less than 1) in add above-mentioned three kinds respectively Demulsifier 10ml, and respectively at 10 DEG C, 25 DEG C, stir 30rad/min at a temperature of 50 DEG C, after reaction 2h, record dehydration rate, As shown in table 3.
Table 3
Embodiment 4
A kind of inorganic-organic hybrid type demulsifier, the mass ratio of the most poly-ferro-silico aluminium and propylene glycol polyethers is 50:100.
A kind of inorganic-organic hybrid type demulsifier, its preparation method comprises the steps:
(1) preparation of activated silicic acid: weigh 90g waterglass and add 500ml water and dissolve under agitation, obtaining waterglass dilute Solution.Measure 1+5 sulphuric acid (1 volume concentrated sulphuric acid+5 volume distilled water shakes up) 1000ml, water glass solution is joined sulphuric acid In solution, simultaneously with the speed high degree of agitation of 120rad/min.Just activated silicic acid is obtained after standing 30min after having reacted.One formula Three parts.
(2) preparation of poly-ferro-silico aluminium: measure the activated silicic acid of 500ml, adds the sulfur of 38g under conditions of 60rad/min stirs Acid aluminum and 18g iron chloride, stop stirring after 30min, after aging 2h, prepares the poly-ferro-silico aluminium of liquid, wherein molal quantity (Al3++Fe3+):SiO3 2-=2:3, Al3+: Fe3+=2:1.In triplicate.
(3) preparation of propylene glycol polyether demulsification agent: propylene glycol 2g and catalyst potassium hydroxide are put in autoclave, uses Air in nitrogen displacement still, under stir speed (S.S.), 60rad/min is warming up to 130 DEG C, adds ring continuously at below pressure 0.3MPa Ethylene Oxide, until 800g, adds oxirane until 480g, continues reaction 2h, lower the temperature and still, obtain propylene glycol polyethers breakdown of emulsion Agent.
(4) preparation of poly-ferro-silico aluminium-propylene glycol polyether demulsification agent: take 100g propylene glycol polyether demulsification agent at normal temperatures and be dissolved in 500ml, 5% methanol solution in, in triplicate, under 80 DEG C of constant temperature, be slowly added dropwise poly-ferro-silico aluminium solution 500ml with 1ml/s (poly-ferro-silico aluminium solution 642g, the most poly-ferro-silico aluminium 49.72g), and stir 240rad/min, just obtain after it is completely dissolved Poly-ferro-silico aluminium-propylene glycol polyether demulsification agent.Stable performance placed for a long time by gained demulsifier.
(5) the petrochemical enterprise oily waste water that green environmental protection is provided in 100mL adds the novel breakdown of emulsion of (4) gained sample Agent 10ml, respectively at 10 DEG C, 25 DEG C, stirs 30rad/min, reacts 30min at a temperature of 50 DEG C, record respectively after 2h, 4h Dehydration rate.As shown in table 4.
Table 4
In sum, the present invention selects poly-ferro-silico aluminium and polyethers demulsifier to react, under conditions of described in summary of the invention, Synthesize the novel demulsifier of inorganic-organic hybrid.This demulsifier consumption is few, range width, effective, rate of water loss is fast And have low-temperature demulsification effect.
The above is only the preferred embodiment of the present invention, for the person of ordinary skill of the art, without departing from this On the premise of bright creation design, it is also possible to make some modifications and variations, and broadly fall into protection scope of the present invention.

Claims (10)

1. an inorganic-organic hybrid type demulsifier, it is characterised in that it comprises poly-ferro-silico aluminium and propylene glycol polyethers, described poly-silicon The mass ratio of ferro-aluminum and propylene glycol polyethers is (49～54): 100.
A kind of inorganic-organic hybrid type demulsifier the most according to claim 1, it is characterised in that described poly-ferro-silico aluminium uses Poly-ferro-silico aluminium solution, poly-ferro-silico aluminium solution manufacturing method can be: according to the chemical expression Fe of poly-ferro-silico aluminiummAln(SiO3)xIn Element of Fe, the mol ratio of Al, Si, weigh iron chloride, aluminum sulfate and modified active silicic acid, then stirred by modified active silicic acid Aluminum sulfate and iron chloride is added under conditions of mixing, after stirring, aging prepared poly-ferro-silico aluminium solution, having of the most poly-ferro-silico aluminium Effect solid content is 5-10%.
A kind of inorganic-organic hybrid type demulsifier the most according to claim 2, it is characterised in that described modified active silicic acid Preparation method be: waterglass is 1:(7～10 with the ratio of water quality), waterglass is dissolved in water, obtains waterglass diluent； Waterglass diluent is joined in sulfuric acid solution, after stirring stands after having reacted, obtains modified active silicic acid.
A kind of inorganic-organic hybrid type demulsifier the most according to claim 3, it is characterised in that described sulfuric acid solution pH Being 0.1～1, waterglass diluent and sulfuric acid solution volume ratio are 1:(1.5～2)；The speed of stirring is 80～120rad/min, stirs The time of mixing is 10～15min, and time of repose is 30min～1h.
A kind of inorganic-organic hybrid type demulsifier the most according to claim 1, it is characterised in that described propylene glycol polyethers Preparation method is: with propylene glycol for initiator and expoxy propane and oxirane hybrid reaction in high pressure, anti-at 110～140 DEG C Should prepare.
A kind of inorganic-organic hybrid type demulsifier the most according to claim 5, it is characterised in that described propylene glycol, epoxy The mass ratio of propane and oxirane is 1:(300～400): (200～240).
7. the preparation method of a kind of inorganic-organic hybrid type demulsifier described in claim 1, it is characterised in that by poly-ferro-silico aluminium Stir at normal temperatures with polyethers demulsifier and mix, i.e. obtain inorganic-organic hybrid type demulsifier.
8. the preparation method of a kind of inorganic-organic hybrid type demulsifier described in claim 1, it is characterised in that propylene glycol is gathered Ether is dissolved in solvent, drips poly-ferro-silico aluminium solution under 70～80 DEG C of temperature, after stirring is completely dissolved to it, obtains inorganic-organic multiple Mould assembly demulsifier.
The preparation method of a kind of inorganic-organic hybrid type demulsifier the most according to claim 8, it is characterised in that described molten It is 30-50% that agent accounts for the mass percent of inorganic-organic hybrid type demulsifier；Rate of addition is 1～100ml/s, and mixing speed is 10～240rad/min.
10. the application process of a kind of inorganic-organic hybrid type demulsifier described in claim 1, it is characterised in that according to inorganic- Organic composite type demulsifier and wastewater volume, than for 1:5-15, stir at 10～50 DEG C and react.
CN201610161119.6A 2016-03-22 2016-03-22 A kind of inorganic-organic hybrid type demulsifier and its preparation, application method Expired - Fee Related CN105800733B (en)

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CN108277041A (en) * 2018-02-26 2018-07-13 四川锦盛油田技术服务有限公司 A kind of gas field adopt defeated water-soluble demulsifier, preparation method and application
CN108893177A (en) * 2018-05-07 2018-11-27 刘帆 A kind of gear oil and preparation method thereof

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CN102876356A (en) * 2011-07-14 2013-01-16 中国石油化工股份有限公司 Demulsifying dehydration method of oilfield produced liquid
CN102897882A (en) * 2012-10-18 2013-01-30 江汉大学 Polysilicate aluminum ferrite flocculant and application thereof in low-temperature low-turbidity water purification

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CN102399577A (en) * 2011-09-28 2012-04-04 中国石油天然气集团公司 Chemical settling dehydration method for thick oil transition zone ageing oil
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CN108277041A (en) * 2018-02-26 2018-07-13 四川锦盛油田技术服务有限公司 A kind of gas field adopt defeated water-soluble demulsifier, preparation method and application
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