CN103937538A - Novel organic chloride-free demulsifier and preparation method thereof - Google Patents
Novel organic chloride-free demulsifier and preparation method thereof Download PDFInfo
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- CN103937538A CN103937538A CN201410119599.0A CN201410119599A CN103937538A CN 103937538 A CN103937538 A CN 103937538A CN 201410119599 A CN201410119599 A CN 201410119599A CN 103937538 A CN103937538 A CN 103937538A
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- emulsion splitter
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- demulsifier
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Abstract
The invention discloses a novel organic chloride-free demulsifier. The novel organic chloride-free demulsifier is formed by carrying out reaction on dimethyl carbonate and polyether in a weight ratio of (1-5):100 at the temperature of 110-120 DEG C in the presence of a catalyst. The preparation method comprises that polyether and the catalyst are stirred in ratio and uniformly heated up to 110-120 DEG C, dimethyl carbonate is dropwise added and refluxing and ageing are carried out, so that a demulsifier product is obtained. The prepared demulsifier has good demulsification property, and organic chloride is not contained in the synthesized demulsifier, so that the problem of organic chloride is solved, and synthesis cost is reduced; and the novel organic chloride-free demulsifier is a green product.
Description
Technical field
The present invention relates to a kind of novel not containing organochlorine emulsion splitter and preparation method thereof.
Background technology
Domestic each elephant has entered ultra-high water-containing development late stage at present, former difficult mining-employed reserves (as high viscous oil, super viscous crude, the poor oil reservoir of geologic condition) is progressively exploitation now, usedly adopt by force injection well stimulation and day by day increase, cause Produced Liquid character in current performance history, compared with primary oil recovery, secondary phase of oil production, significant change has occurred, the particularly extensive enforcement of tertiary oil recovery, make Produced Liquid character more complicated, this brings larger difficulty also to ground profit processing.As the introducing of various tensio-active agents in acidizing treatment, the employing of water-soluble polymer frozen glue in plug water construction, and the extensive use of emulsifying and viscosity-reducing agent for condensed oil, alkali, polymkeric substance, tensio-active agent ternary composite driving have become the important means of stable yields volume increase at each elephant.The enforcement of these measures, makes the easier Produced Liquid of former dehydration form metastable emulsion system, and this brings more hang-up to crude oil demulsification dehydration, forms many new problems, as the profit processing of tertiary oil recovery produced liquid; The Application and Development of thick oil demulsifier; The research application of shallow oil reservoir low-temperature demulsifying agent etc.In the solution process of these problems, all there is an outstanding feature, require emulsion splitter to possess efficient dehydration breakdown of emulsion ability.
The conventional emulsion splitter of domestic emulsion splitter industry is polyethers, is the breaking emulsion and dewatering effect that improves emulsion splitter, conventionally adopts cross policy " change head, change tail, add bone, chain extension, grafting " to improve adaptability and the specific aim of emulsion splitter.Wherein, crosslinking reaction is a kind of most popular method that improves molecular weight, and linking agent used comprises PoCl and TDI now.And because TDI cost is relatively high, larger to harm, belong to control product; PoCl reaction temperature and, reaction is easy to control, cost is lower, it is now domestic that mainly to carry out emulsion splitter with PoCl crosslinked.But along with the exploitation in oil field, occur that again the organochlorine that new problem: PoCl introduces has a certain impact to the oil refining device in downstream.Because the content of organochlorine in natural crude oil is very low, the source that enters most organochlorines in the crude oil of refinery is the chemical assistant (as clear anti-waxing agent etc.) using in Oil extraction process, there are a series of hydrolysis reaction owing to being recognized that organochlorine enters the catalytic cracking unit of refinery with crude oil after, the equipment of catalytic fractionator is produced to corrosion, and deposition causes disturbance even to destroy to the normal running of tower under suitable condition.Therefore, in order to prevent the appearance of this type of phenomenon, the prerequisite that reduces the content of organic chloride in crude oil is the exogenous organochlorine reducing in the defeated process of extracting, gathering, demulsifier product is as the one of crude Treatment agent, its most of product has adopted PoCl as linking agent, has caused the exogenous increase of product content of organic chloride.In view of above situation, this problem is mainly studied and is used the not alternative TDI of novel crosslinker and the PoCl containing organochlorine to be cross-linked emulsion splitter, researches and develops its crosslinking process, substitutes existing chloride linking agent completely, obtains the novel emulsion splitter that does not contain organochlorine.
Existing patent report methylcarbonate (DMC) and aliphatic diol carry out transesterification reaction and prepare oligocarbonate diols, and the catalyzer adopting has tetraisopropoxy titanium, ytterbium (III) acetylacetonate compound etc.Above patent alcohol used is all long chain diol, does not at present also carry out transesterify for polyethers.According to the data analysis to grasp, choosing methylcarbonate is that linking agent, Z material are catalyzer crosslinked polyethers emulsion splitter.So fundamentally solved the circumscribed predicament of linking agent, thereby the present invention will become emphasis and the direction of emulsion splitter industry development at economy, safety, environmental protection, the aspect such as inexpensive, efficient.
Summary of the invention
The invention provides a kind of novel emulsion splitter that does not contain organochlorine and preparation method thereof.
First object of the present invention is to provide one can replace epoxy chloropropane (PoCl) and TDI etc. to do the raw material of linking agent;
Second object of the present invention is that a kind of linking agent that does not contain organochlorine will be provided;
The 3rd object of the present invention is that a kind of catalysis DMC good catalyst of crosslinked emulsion splitter will be provided.
Technical scheme of the present invention:
Novel not containing the emulsion splitter of organochlorine, it is characterized in that: its by methylcarbonate and polyethers by weight the ratio of 1～5:100 under the catalysis of catalyzer, at 110 DEG C～120 DEG C of temperature, react and form.
The described a kind of novel preparation method who does not contain the emulsion splitter of organochlorine, is characterized in that, comprises the following steps:
Quantitative uncrosslinked polyethers is placed in to the reactor that mechanical stirrer is housed, under agitation add quantitative catalyzer, by heating material to 100 DEG C, then pass into nitrogen replacement, vacuum hydro-extraction, while distillating to exclusion, close vacuum valve, make pressure in still approach-0.08～-0.10Mpa, heating systems makes temperature slowly rise to 120 DEG C, drips quantitative methylcarbonate (DMC), reaction 1-1.5h, finish heating, cooling, blowing obtains emulsion splitter, and wherein, the add-on of methylcarbonate is the 1%-3% of polyethers quality.
Described polyethers is to be the polymkeric substance that main raw material is polymerized by oxyethane EO and propylene oxide PO.
Described catalyzer is selected from the mixture of the one or both in highly basic, sodium alkoxide, and the add-on of catalyzer is 5 ‰ of polyethers quality～10 ‰.
Beneficial effect of the present invention is:
The present invention adopts material carbon dimethyl phthalate cheap and easy to get (DMC) and common polyether demulsification agent under middle temperature, to carry out the synthesizing cross-linked type emulsion splitter of transesterification reaction, with environmental protection and do not replace traditional epoxy chloropropane (PoCl), TDI to prepare the more emulsion splitter of high surface containing the methylcarbonate (DMC) of organochlorine, greatly reduce the limitation of existing linking agent like this.Making it have degradability and be bumped into carbonate group in this type of cross-linking type emulsion splitter chain, is the important directions of current environmental protection development.The more important thing is that one aspect of the present invention has improved the breakdown of emulsion ability of existing emulsion splitter, be satisfied with rig-site utilization, ensure the normal operation of joint station, on the other hand, ensured can not introduce organochlorine in production process, can not cause corrosion to downstream refinery device.
Brief description of the drawings
Fig. 1 is the reaction mechanism figure of methylcarbonate and polyethers;
Fig. 2 is the reaction process schematic diagram of methylcarbonate and polyethers.
Embodiment
Below in conjunction with embodiment, further illustrate novel preparation method and the performance test results that does not contain organochlorine emulsion splitter, but the present invention is not limited to these embodiment.
Embodiment 1
Dry uncrosslinked 2000kg polyethers agent is placed in to the reactor that mechanical stirrer is housed, under agitation add 10kg alcohol sodium catalyst, heating material to 100 DEG C, nitrogen replacement, vacuum hydro-extraction (approximately needing 0.5h), when distillating to exclusion, close vacuum valve, make pressure in still approach-0.08～-0.10Mpa, temperature slowly rises to 120 DEG C, and in 30min, drips 20kg methylcarbonate (DMC), experiment reaction 1h finishes heating, and cooling, blowing obtains emulsion splitter.Analyze after tested to such an extent that the absolute dehydration rate of emulsion splitter is 96.19%.
Embodiment 2
Dry uncrosslinked 1500kg polyethers agent is placed in to the reactor that mechanical stirrer is housed, under agitation add 15kg alcohol sodium catalyst, heating material to 100 DEG C, nitrogen replacement, vacuum hydro-extraction (approximately needing 0.5h), when distillating to exclusion, close vacuum valve, make pressure in still approach-0.08～-0.10 Mpa, temperature slowly rises to 120 DEG C, and in 30min, drips 45kg methylcarbonate (DMC), experiment reaction 1h finishes heating, and cooling, blowing obtains emulsion splitter.Analyze after tested to such an extent that the absolute dehydration rate of emulsion splitter is 97.10%.
Embodiment 3
Dry uncrosslinked 6000kg polyethers agent is placed in to the reactor that mechanical stirrer is housed, under agitation add 60kg alcohol sodium catalyst, heating material to 100 DEG C, nitrogen replacement, vacuum hydro-extraction (approximately needing 0.5h), when distillating to exclusion, close vacuum valve, make pressure in still approach-0.08～-0.10 Mpa, temperature slowly rises to 120 DEG C, and in 45min, drips 100kg methylcarbonate (DMC), experiment reaction 1h finishes heating, and cooling, blowing obtains emulsion splitter.Analyze after tested to such an extent that the absolute dehydration rate of emulsion splitter is 91.27%.
Embodiment 4
Dry uncrosslinked 8000kg polyethers agent is placed in to the reactor that mechanical stirrer is housed, under agitation add 40kg alkali catalyst, heating material to 100 DEG C, nitrogen replacement, vacuum hydro-extraction (approximately needing 0.5h), when distillating to exclusion, close vacuum valve, make pressure in still approach-0.08～-0.10 Mpa, temperature slowly rises to 115 DEG C, and in 60min, drips 200kg methylcarbonate (DMC), experiment reaction 1h finishes heating, and cooling, blowing obtains emulsion splitter.Analyze after tested to such an extent that the absolute dehydration rate of emulsion splitter is 98.61%.
Embodiment 5
Dry uncrosslinked 2000kg polyethers agent is placed in to the reactor that mechanical stirrer is housed, under agitation add 15kg base metal catalysts, heating material to 100 DEG C, nitrogen replacement, vacuum hydro-extraction (approximately needing 0.5h), when distillating to exclusion, close vacuum valve, make pressure in still approach-0.08～-0.10Mpa, temperature slowly rises to 115 DEG C, and in 30min, drips 50kg methylcarbonate (DMC), experiment reaction 1h finishes heating, and cooling, blowing obtains emulsion splitter.Analyze after tested to such an extent that the absolute dehydration rate of emulsion splitter is 92.15%.
Embodiment 6
Dry uncrosslinked 7500kg polyethers agent is placed in to the reactor that mechanical stirrer is housed, under agitation add 45kg composite catalyst, heating material to 100 DEG C, nitrogen replacement, vacuum hydro-extraction (approximately needing 0.5h), when distillating to exclusion, close vacuum valve, make pressure in still approach-0.08～-0.10Mpa, temperature slowly rises to 115 DEG C, slowly drips 180kg methylcarbonate (DMC) according to speed of response, experiment reaction 1h finishes heating, and cooling, blowing obtains emulsion splitter.Analyze after tested to such an extent that the absolute dehydration rate of emulsion splitter is 93.28%.
Claims (4)
1. novel not containing the emulsion splitter of organochlorine, it is characterized in that: its by methylcarbonate and polyethers by weight the ratio of 1～5:100 under the catalysis of catalyzer, at 110 DEG C～120 DEG C of temperature, react and form.
2. a kind of novel preparation method who does not contain the emulsion splitter of organochlorine as claimed in claim 1, is characterized in that, comprises the following steps:
Quantitative uncrosslinked polyethers is placed in to the reactor that mechanical stirrer is housed, under agitation add quantitative catalyzer, by heating material to 100 DEG C, then pass into nitrogen replacement, vacuum hydro-extraction, while distillating to exclusion, close vacuum valve, make pressure in still approach-0.08～-0.10Mpa, heating systems makes temperature slowly rise to 120 DEG C, drips quantitative methylcarbonate (DMC), reaction 1-1.5h, finish heating, cooling, blowing obtains emulsion splitter, and wherein, the add-on of methylcarbonate is the 1%-3% of polyethers quality.
3. according to a kind of novel emulsion splitter that does not contain organochlorine described in claim 1, it is characterized in that, described polyethers is to be the polymkeric substance that main raw material is polymerized by oxyethane EO and propylene oxide PO.
4. according to a kind of novel emulsion splitter that does not contain organochlorine described in claim 1, it is characterized in that described catalyzer is selected from the mixture of the one or both in highly basic, sodium alkoxide, the add-on of catalyzer is 5 ‰ of polyethers quality～10 ‰.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410119599.0A CN103937538A (en) | 2014-03-27 | 2014-03-27 | Novel organic chloride-free demulsifier and preparation method thereof |
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| CN201410119599.0A CN103937538A (en) | 2014-03-27 | 2014-03-27 | Novel organic chloride-free demulsifier and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1522270A (en) * | 2001-06-27 | 2004-08-18 | Process for producing aliphatic oligocarbonate diols | |
| CN1807557A (en) * | 2006-01-09 | 2006-07-26 | 长江(扬中)电脱盐设备有限公司 | Composite oil-soluble demulsifier product and its production method |
| US20100273690A1 (en) * | 2006-08-11 | 2010-10-28 | Holt David G L | Synergistic combination of demulsifiers for enhancing demulsification properties in industrial lubricants |
| CN102558542A (en) * | 2011-12-09 | 2012-07-11 | 东南大学 | Method for preparing sucrose polyether carbonate polyol |
| CN102558533A (en) * | 2011-12-09 | 2012-07-11 | 东南大学 | Preparation method of polyether carbonate polyalcohol |
-
2014
- 2014-03-27 CN CN201410119599.0A patent/CN103937538A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1522270A (en) * | 2001-06-27 | 2004-08-18 | Process for producing aliphatic oligocarbonate diols | |
| CN1807557A (en) * | 2006-01-09 | 2006-07-26 | 长江(扬中)电脱盐设备有限公司 | Composite oil-soluble demulsifier product and its production method |
| US20100273690A1 (en) * | 2006-08-11 | 2010-10-28 | Holt David G L | Synergistic combination of demulsifiers for enhancing demulsification properties in industrial lubricants |
| CN102558542A (en) * | 2011-12-09 | 2012-07-11 | 东南大学 | Method for preparing sucrose polyether carbonate polyol |
| CN102558533A (en) * | 2011-12-09 | 2012-07-11 | 东南大学 | Preparation method of polyether carbonate polyalcohol |
Non-Patent Citations (1)
| Title |
|---|
| 李岿等: "清水型特（超）稠油破乳剂及其合成方法", 《精细与专用化学品》 * |
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Application publication date: 20140723 |