CN1088043C - Demulsification type organic flocculant and preparation process thereof - Google Patents
Demulsification type organic flocculant and preparation process thereof Download PDFInfo
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- CN1088043C CN1088043C CN 98121074 CN98121074A CN1088043C CN 1088043 C CN1088043 C CN 1088043C CN 98121074 CN98121074 CN 98121074 CN 98121074 A CN98121074 A CN 98121074A CN 1088043 C CN1088043 C CN 1088043C
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- flocculation agent
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- amido
- hydroxyalkyl
- flocculant
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Abstract
The present invention relates to a demulsifying organic flocculant and a preparing method thereof. The general structure of the flocculant is shown like the right formula; R1, R2, R4 and R6 represents an H or hydroxyalkyl of C<1-3>; R3 represents amido or substituted amino with hydroxyalkyl; R5 and R8 represents alkylidene; R7 represents carbonyl oxygen or hydroxyl group alkyl oxygen. The flocculant which can be used for treating oily sewage has the characteristics of small using amount, small generated dregs amount, high demulsifying performance and wide adaptability.
Description
The present invention relates to a kind of organic floculant of handling oily(waste)water and preparation method thereof that is used to.
In petroleum refining process, produce a large amount of oily(waste)waters, adopt the technological process of gravity oil removal-dissolved air floatation-bio-oxidation to handle this sewage usually.Remove with emulsified state or unbound state and be dispersed in organic pollutant in the sewage by adding the chemical flocculation agent method at flotation cells.Along with the stock oil change of refining of petroleum industry processing is heavy, the emulsification degree of the oily(waste)water that produces constantly increases the weight of, use single inorganic polymeric aluminum (PAC) to be difficult to reach the ideal water quality requirement, the flocculation agent that this exploitation is had good demulsification performance and flocculation ability is efforts at environmental protection person's a top priority.
United States Patent (USP) 4990262 is introduced with formaldehyde and dicyanamide polycondensate and is handled the ore pulp flocculation dewatering; United States Patent (USP) 4271028 is introduced with formaldehyde and the processing of dicyanamide polycondensate and is contained the protein waste liquid, and effect is better.Though this polymkeric substance has good demulsification when being used to handle the petrochemical complex oily(waste)water, the synthetic cost of flocculation agent is higher, brings certain difficulty to promotion and application.
The object of the present invention is to provide a kind of lower-cost demulsification type cationic flocculant and preparation method thereof, when this agent is used for oily water treatment, have consumption little, produce that slag is few, demulsification performance strong, the characteristics of wide adaptability, under the prerequisite that does not change present sewage treatment facility, can substitute present widely used inorganic flocculating agent, improve oil removal efficiency.
Demulsification type cationic flocculant of the present invention is to add excessive formaldehyde with formaldehyde or acetaldehyde preparing on the basis of flocculating agent A with amine or their salt such as polycondensations such as cyanamide salt, Dyhard RU 100 or guanidinesalt under the acidic medium effect existing, and excessive aldehyde can obtain rerum natura and the very approaching flocculating agent B of demulsification performance with A with urea or thiocarbamide repolymerization again in the base.Owing in the process of synthetic B, do not increase the feed ratio of the more expensive amine of price, make the synthesis material cost that improves back gained flocculating agent B reduce 18%-25% than A.
Wherein the general formula of flocculation agent product A is:
R wherein
1Be methylol methyl or hydroxyethyl; R
2Be hydrogen or methylol or C
1～3Alkyl, R
3Can be an amido, also can be the amido that has methylol or hydroxyethyl replacement, R
4Be hydrogen or methylol or C
1～3Alkyl.R
5Can be methylene radical, also can be ethylidene.
The present invention realizes its modification and reduces raw materials cost by adding the 3rd component urea on the basis of flocculating agent A, in the building-up process of flocculating agent A, excessive formaldehyde or acetaldehyde have been added, with the 3rd component urea and excessive aldehyde reaction, form corresponding hydroxyurea i.e. an Oxymethurea, dimethylolpropionic urea or a hydroxyl ethyl urea, dihydroxy ethyl urea, its general formula is
R wherein
6Be hydrogen or methylol or C
1～3Alkyl, R
7Be carbonyl or methylol, hydroxyethyl, R
8Be methylene radical, or ethylidene.
Because all there is active group at the hydroxyurea two ends, under the acidic medium condition, they with flocculating agent A in reactive group generation repolymerization, the formation flocculating agent B.Its general formula is:
No matter find that in triturating of the present invention its preparation process has very big difficulty, be to add urea behind synthetic flocculant A again, still adds urea in synthetic A and all can not obtain transparent viscous fluid of the present invention.Find only in the process of synthetic A, to add excessive aldehyde by a large amount of experiments, add urea afterwards again and could form demulsification type cationic flocculant of the present invention.Its preparation process comprises:
At first one have stir and the reactor of cooling system in synthesize a kind of colourless non-linear lower molecular weight flocculating agent A.Building-up process is: add aldehyde compound a in reactor earlier, as formaldehyde or acetaldehyde etc., under stirring state, add aminated compounds b, as quadrol, dicyanamide etc., add ammonium chloride c then, reacted 1～24 hour under 40～150 ℃ of conditions, 80～110 ℃ were reacted 2～8 hours down more fortunately, formed a kind of colourless non-linear lower molecular weight flocculant polymer A.Because reaction product A contains the raw material b of higher proportion, so its cost is higher.The invention reside in the building-up process of finishing polymer A, under the prerequisite of the feed ratio that does not improve raw material b, after the add-on of cheap a of improving price, add compound d such as a kind of originate wide, low-cost urea or thiocarbamide and excessive a again the repolymerization reaction takes place under 50～150 ℃ of conditions, form new flocculating agent B.Breakdown of emulsion and deoiling effect when the physicals of B and processing oily(waste)water are very close with former flocculating agent A.Wherein various quality of material proportionings are b: a=1: 1.0～1: 10, be preferably b: a=1: 2.5～1: 5; B: c=1: 0.5～1: 2, be preferably b: c=1: 0.8～1: 1.5; B: d=1: 0.1～1: 1.5, be preferably b: d=1: 0.5～1: 1.This polymkeric substance has polyfunctional groups such as hydroxyl, amido, the electric density height, and breakdown of emulsion is strong, characteristics such as moderate cost, good water solubility.
Advantage of the present invention is by the repolymerization mode wide, the low-cost another kind of component in source to be joined in the flocculation agent, makes the flocculation agent of new formation have the effect of breakdown of emulsion, flocculation, bridge formation equally.The more former flocculating agent A of flocculating agent B has bigger reduction on synthetic cost.Both may be used solely to handle oily(waste)water.Also can all can when handling oily(waste)water, show good demulsification performance and deoiling effect with the composite use of the flocculation agent of other type.
When it and inorganic polymeric aluminum PAC were composite, its use cost can also reduce; When it and this amides of polypropylene polymeric flocculant are composite, can make the flco of formation become big, separate rapidly with water.Be more significantly, formed scum silica frost oleaginousness height behind the adding polymeric flocculant, water ratio is low, and the scum silica frost growing amount reduces.
Following example is used for further specifying the advantage of flocculation agent of the present invention.
Comparative example 1
In a glass there-necked flask that has stirring, thermometer and a backflow facility, adding concentration is 37% formaldehyde 160 grams, add 81 gram Dyhard RU 100s again, stirring makes the dissolving of solid Dyhard RU 100, add 53 gram ammonium chlorides subsequently, reactor heating makes temperature be raised to 95 ℃, and keeps on this temperature of reaction 3 hours, and reaction finishes the postcooling product and obtains water white transparency flocculation agent 1.
Example 1
In the equipment that in as comparison 1, is adopted, add the acetaldehyde of 214 grams and the Dyhard RU 100 of 81 grams, stirring makes the Dyhard RU 100 dissolving, add 53 gram ammonium chlorides again, treat that ammonium chloride adds the back that finishes and improves temperature of reaction to 110 ℃, reaction continue to add again after 2.5 hours thiocarbamide 13 grams and under this temperature of reaction 2 hours dope products of reaction, be flocculation agent 2 after the modification.
Example 2
In a there-necked flask that has stirring system, thermometer and a prolong, add formaldehyde 205 grams and 81 gram Dyhard RU 100s, treat that Dyhard RU 100 dissolving back adds ammonium chloride 37 grams, then add urea 18 grams, flocculant product 3 after 97 ℃ reaction promptly got modification in 3 hours down.
Example 3
As adding concentration in the above-mentioned example is 37% formaldehyde 240 grams and 81 gram Dyhard RU 100s, make the Dyhard RU 100 dissolving after, add 48 gram ammonium chlorides and 30 and restrain ureas, improve bath temperature to 95 ℃ afterwards.And under this temperature, reacted again 4 hours, promptly get flocculation agent 4 after the modification after the cooling.
Example 4
In there-necked flask, add 187 and restrain formaldehyde and 81 Dyhard RU 100s that restrain, 63.6 gram ammonium chlorides are warmed up to 90 ℃ of reactions 4 hours, add 6 gram ureas therebetween, get product flocculation agent 5.
Example 5
In three mouthfuls of reaction flasks, adding concentration is 37% formaldehyde 285 grams, the Dyhard RU 100s and the 53 gram ammonium chlorides of 81 grams, adds 48 gram ureas subsequently again, is warmed up to 97 ℃ of reactions 4 hours, product flocculation agent 6.
Example 6
Reaction process and employed medicament are the same, add formaldehyde 295 grams, Dyhard RU 100 81 grams, control reaction temperature adds 68 gram ammonium chlorides under 55 ℃ condition, be warmed up to 110 ℃ and reacted 2 hours, add urea 60 grams, under this temperature, continue reaction and got product flocculation agent 7 in 4 hours.The composition of flocculation agent in each example of table 1:
| Form wt% | Comparative Examples 1 | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Formaldehyde | 54.4 | 59.3 | 60.1 | 60.2 | 55.4 | 61.1 | 58.4 |
| Dyhard RU 100 | 27.6 | 22.4 | 23.7 | 20.3 | 24.0 | 17.3 | 16.0 |
| Ammonium chloride | 18 | 14.6 | 10.9 | 12.0 | 18.8 | 11.3 | 13.7 |
| Urea | 3.6 | 5.3 | 7.5 | 1.8 | 10.3 | 11.9 | |
| Total mass (gram) | 294 | 361 | 341 | 399 | 337.6 | 467.5 | 504.3 |
Example 7
With flocculation agent 1 in the comparative example 1 as a comparison sample compare with sample of the present invention respectively, table 2 result is flocculation agent 1 and the result of flocculation agent 5 of the present invention to certain refinery oily(waste)water
The treatment effect of table 2 flocculation agent 1 and 5 pairs of refinery's oily(waste)waters of flocculation agent
| The flocculation agent title | Dosage mg/l | Oil-contg mg/l | Oil removal rate | Remarks | |
| Former water | Water outlet | ％ | |||
| Flocculation agent 1 | 10 | 525 | 16.6 | 96.8 | Breakdown of emulsion, water colour clarification |
| Flocculation agent 1 | 20 | 525 | 13.9 | 97.4 | Breakdown of emulsion, water colour clarification |
| Flocculation agent 1 | 30 | 525 | 11.6 | 97.8 | Breakdown of emulsion, water colour clarification |
| Flocculation agent 5 | 10 | 525 | 17.1 | 96.7 | Breakdown of emulsion, water colour clarification |
| Flocculation agent 5 | 20 | 525 | 14.2 | 97.2 | Breakdown of emulsion, water colour clarification |
| Flocculation agent 5 | 30 | 525 | 13.5 | 97.4 | Breakdown of emulsion, water colour clarification |
Example 8
The treatment effect of table 3 flocculation agent 1 and 3 pairs of oil-contaminated water of oil field of flocculation agent
| The flocculation agent title | Dosage mg/l | Oil-contg mg/l | Oil removal rate | Remarks | |
| Former water | Water outlet | ％ | |||
| Flocculation agent 1 | 20 | 268 | 81.6 | 69.6 | Water outlet is more turbid |
| Flocculation agent 1 | 30 | 268 | 56.0 | 79.1 | Water outlet is clear |
| Flocculation agent 1 | 40 | 268 | 41.6 | 84.5 | Water outlet is transparent |
| Flocculation agent 3 | 20 | 268 | 82.0 | 69.4 | Water outlet is more turbid |
| Flocculation agent 3 | 30 | 268 | 46.2 | 82.8 | Water outlet is clear |
| Flocculation agent 3 | 40 | 268 | 37.2 | 86.1 | Water outlet is transparent |
Example 9
Table 4 flocculation agent 1 and flocculation agent 3,5,6 treatment effects to certain refinery's oily(waste)water
Flocculant dosage oil-contg mg/l oil removal rate
The former water water outlet of title mg/l %
Flocculation agent 1 20 79 20.5 74.0
Flocculation agent 1 40 79 21.3 73.0
Flocculation agent 1 60 79 18.5 76.6
Flocculation agent 4 20 79 23.8 69.9
Flocculation agent 4 40 79 20.7 73.8
Flocculation agent 4 60 79 10.1 87.2
Flocculation agent 6 20 79 18.0 77.2
Flocculation agent 6 40 79 19.0 75.9
Flocculation agent 6 60 79 17.5 77.8
Flocculation agent 7 20 79 21.3 73.0
Flocculation agent 7 40 79 20.1 74.6
Flocculation agent 7 60 79 18.5 76.6
Visible flocculation agent 2,3,4,5,6 and 7 pairs of refineries of flocculation agent and oil-contaminated water of oil field all have effect of demulsification and oil removal preferably from table 2 to table 4, flocculation agent 3 after modification, flocculation agent 4, flocculation agent 56,7 its deoiling effects and contrast flocculation agent 1 are very nearly the same, and the deoiling effect that has has surpassed flocculation agent 1.And urea that example 1～example 6 is added or thiocarbamide are not wait, but all show good deoiling effect, this further specifies and adds the deoiling effect that urea and thiocarbamide not only do not influence flocculation agent, and synthetic product deoiling effect is not worse than Comparative Examples 1 under some condition.The synthetic cost of its raw material reduces by 18%～25% than example 1.
Claims (8)
1, a kind of demulsification type organic flocculant contains in the structure
It is characterized in that containing
, form following structural formula material:
R wherein
1, R
2, R
4, R
6Be respectively H or C
1～3Wherein any one of hydroxyalkyl; R
3Be amido or the amido that has the hydroxyalkyl replacement; R
5, R
8It is respectively alkylidene group; R
7Be ketonic oxygen or hydroxyalkyl oxygen; M=5～15, n=10～20.
2, according to the described flocculation agent of claim 1, it is characterized in that described R
1, R
2, R
4, R
6Be methylol or hydroxyethyl.
3, according to claim 1 or 2 described flocculation agents, it is characterized in that described R
3Be amido, the amido that has methylol or the amido that has hydroxyethyl.
4, according to right general introduction 1 or 2 described flocculation agents, it is characterized in that described R
5, R
8Be respectively methylene radical or ethylidene.
5, according to claim 1 or 2 described flocculation agents, it is characterized in that described R
7Be ketonic oxygen, hydroxyl methoxyl group or hydroxyl-oxethyl.
6, a kind of method for preparing organic floculant comprises:
(1), one have stir and the reactor of cooling system in add aldehyde compound (a) earlier;
(2), under stirring state, add aminated compounds (b);
(3), add ammonium chloride (c), under 40～150 ℃ of conditions, reacted 1～24 hour, form a kind of colourless non-linear lower molecular weight flocculant polymer A;
(4), add carbamide compounds (d) and repolymerization takes place under 50～150 ℃ of conditions react, form new flocculating agent B;
Wherein various quality of material proportionings are b: a=1: 1.0～1: 10; B: c=1: 0.5～1: 2; B: d=1: 0.1～1: 1.5; Wherein said aldehyde compound (a) is formaldehyde or acetaldehyde, and aminated compounds (b) is quadrol, dicyanamide, and said carbamide compounds is urea or thiocarbamide.
7, according to the described preparation method of claim 6, the quality proportioning that it is characterized in that each material is b: a=1: 2.5～1: 5, b: c=1: 0.8～1: 1.5, and b: d=1: 0.5～1: 1.
8,, it is characterized in that reaction times and the temperature in the step (3) is reaction under 80～110 ℃ 2～8 hours according to the described preparation method of claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98121074 CN1088043C (en) | 1998-12-16 | 1998-12-16 | Demulsification type organic flocculant and preparation process thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98121074 CN1088043C (en) | 1998-12-16 | 1998-12-16 | Demulsification type organic flocculant and preparation process thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1257044A CN1257044A (en) | 2000-06-21 |
| CN1088043C true CN1088043C (en) | 2002-07-24 |
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| CN 98121074 Expired - Lifetime CN1088043C (en) | 1998-12-16 | 1998-12-16 | Demulsification type organic flocculant and preparation process thereof |
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| CN108579132A (en) * | 2018-05-15 | 2018-09-28 | 唐山清正环保科技有限公司 | A kind of high efficient reverse-phase emulsifier and preparation method thereof |
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- 1998-12-16 CN CN 98121074 patent/CN1088043C/en not_active Expired - Lifetime
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Granted publication date: 20020724 |