EP2622041A1 - Procédé de séparation de polymères inhibiteurs cinétiques d'hydrates - Google Patents

Procédé de séparation de polymères inhibiteurs cinétiques d'hydrates

Info

Publication number
EP2622041A1
EP2622041A1 EP11761076.6A EP11761076A EP2622041A1 EP 2622041 A1 EP2622041 A1 EP 2622041A1 EP 11761076 A EP11761076 A EP 11761076A EP 2622041 A1 EP2622041 A1 EP 2622041A1
Authority
EP
European Patent Office
Prior art keywords
hydrate inhibitor
kinetic hydrate
process according
inhibitor polymer
aqueous mixture
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.)
Withdrawn
Application number
EP11761076.6A
Other languages
German (de)
English (en)
Inventor
Guillo Alexander Schrader
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Priority to EP11761076.6A priority Critical patent/EP2622041A1/fr
Publication of EP2622041A1 publication Critical patent/EP2622041A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/024—Oxides
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/22—Hydrates inhibition by using well treatment fluids containing inhibitors of hydrate formers

Definitions

  • the present invention is directed to a process for separating kinetic hydrate inhibitor polymers having a molecular weight of at least 1000 Da from an aqueous mixture further comprising hydrocarbons and salts.
  • Low-boiling hydrocarbons such as methane, ethane, propane, butane and iso-butane
  • conduits which are used for the transport and processing of natural gas and crude oil. If a substantial amount of water also is present, it is possible that the water/ hydrocarbon mixture form gas hydrate crystals under conditions of low temperature and elevated pressure.
  • Gas hydrates are clathrates (inclusion compounds) in which small hydrocarbon molecules are trapped in a lattice consisting of water molecules. As the maximum temperature at which gas hydrates can be formed strongly depends on the pressure of the system, hydrates are markedly
  • Melting point depressants also are referred to as
  • thermodynamic hydrate inhibitors thermodynamic hydrate inhibitors.
  • kinetic hydrate inhibitors which prevent the formation of hydrates on a macroscopic scale, i.e. as observable by the naked eye
  • hydrate anti-agglomerants which are capable of preventing agglomeration of hydrate crystals.
  • already small amounts of kinetic hydrate inhibitors or hydrate anti-agglomerants are normally effective in preventing the blockage of a conduit by hydrates.
  • Liquefied natural gas is natural gas (predominantly methane) that has been converted temporarily to liquid form for ease of storage or transport.
  • the actual practice of removing these compounds is quite complex but usually involves condensate removal, water removal, separation of natural gas liquids and sulfur containing compounds and carbon dioxide removal.
  • hydrate inhibitor polymers are often added to raw natural gas streams before pipeline transport or any further treatment. These hydrate inhibitor polymers generally are separated and removed before liquefaction as there they can create problems such as depositing on heat exchanger equipment. Furthermore, the presence of hydrate
  • treatment as such treatment may not be able to deal with these polymers in that the polymers may be poorly bio- degradable and/or tend to block the pores of water treatment filtration equipment.
  • hydrate inhibitor polymers have the property that their solubility in water decreases with increasing temperature and therefore they exhibit reverse solubility versus temperature behavior. This phenomenon is especially well known for glycols.
  • the cloud point temperature of hydrate inhibitor polymers is the temperature above which the mixture starts to phase separate and two phases appear for a given polymer concentration and at given salinity. There are even less methods for removing these kinds of polymers as their removal is restricted by the maximum operating temperature which can be applied.
  • US-A-2008/0312478 describes a method for removing kinetic inhibitors from an aqueous phase which method involves heating the aqueous phase to a temperature above the boiling point of the water. This separation method is disadvantageous from an energy efficiency point of view while it could lead to problems in removing a polymer having a cloud point below the distillation temperature.
  • concentration of kinetic hydrate inhibitor polymer is at most 20 % of the kinetic hydrate inhibitor polymer concentration of the aqueous mixture. It is preferred that the concentration of hydrate inhibitor polymer of the permeate is at most 15 %, more preferably at most 10 %, more specifically at most 5 % of the kinetic hydrate inhibitor polymer as present in the aqueous mixture.
  • the membranes preferably are ceramic membranes, more specifically refractory oxide membranes, most preferably zirconia and/or titania ceramic membranes. Ceramic membranes which have been found to be especially
  • preferred for use in the present invention are those having a pore diameter of at least 0.7 nm, more
  • the pore diameter is at most 3.5 nm, more specifically at most 3.3 nm, most specifically at most 3.1 nm.
  • the pore diameter is
  • membranes which have been found to be suitable are titania membranes having an average pore diameter of from 0.9 nm up to and including 1.0 nm and zirconia ceramic membranes having an average pore diameter of 3.0 nm. The choice of the pore size is determined by the pressure drop over the membrane which is acceptable and the amount of feed to be recovered as permeate .
  • a further advantage of the above process is that it has been found that by choosing the right pore diameter for the membrane, hydrocarbons can be removed besides the kinetic hydrate inhibitor polymer while salts are allowed through.
  • the presence of hydrocarbons in the retentate is advantageous in that it makes the permeate water even purer.
  • the hydrocarbonaceous retentate comprising kinetic hydrate inhibitor polymer can either be sent to an incinerator, wet air oxidation unit, supercritical water oxidation unit or be recycled. Recycling has the
  • hydrocarbons will become part of the hydrocarbonaceous phase instead of the aqueous phase.
  • Another advantage of the process according to the present invention is that salts can be removed as part of the permeate.
  • the salts are separated from the kinetic hydrate inhibitor polymer which prevents build-up of salts in case of recycling the kinetic hydrate inhibitor polymer.
  • the retentate generally will be a kinetic hydrate inhibitor polymer containing water/hydrocarbon mixture.
  • the exact amount of water in the retentate depends on the process conditions applied. If the viscosity of the retentate is high, it can be preferred to add solvent to the retentate before it is processed further such as by recycling .
  • the kinetic hydrate inhibitor polymer for use in the present invention preferably is a water-soluble polymer having a molecular weight of at least 1000 Da, preferably of at least 1500 Da, more specifically at least 2000 Da, more preferably at least 3000 Da.
  • the molecular weight is the weight average molecular weight which can be
  • a further characteristic of hydrate inhibitor polymers is that they inhibit hydrocarbon molecules becoming trapped in a water lattice.
  • the structure of such compounds can vary widely.
  • these polymers are water-soluble polymers containing at least one amide group, preferably comprising a plurality of amide groups.
  • the polymers can be either homopolymers or copolymers containing amide groups.
  • the kinetic hydrate inhibitor polymers preferably are polyamides and/or polyester amides.
  • the expression polymers indicates any large molecule having the
  • Such polymer can contain a large number of small repeat units.
  • An example of a linear polyamide hydrate inhibitor polymer is polyvinyl pyrrolidone.
  • the polymer can be a hyper- branched, also referred to as dendritic, polymer which is functionalized to provide the necessary properties.
  • Preferred hydrate inhibitors are dendrimeric
  • a branch is composed of structural units which are bound radially to the core and which extend outwards.
  • the structural units have at least two reactive monofunctional groups and/or at least one monofunctional group and one multifunctional group.
  • the term multifunctional is understood as having a
  • hydrate inhibitors are dendrimeric polyester amides, more specifically those as described in WO-A-2001/77270.
  • HYBRANE S1200 and HYBRA E HA1300 are especially preferred. These compounds are commercially obtainable from DSM, Geleen, the
  • the dendrimeric compounds as a solution of the compound in an organic solvent such as an alcohol .
  • the separation of kinetic hydrate inhibitor polymers can be carried out under process conditions
  • the pressure perpendicular to the membrane at the retentate side preferably is at most 60 bara.
  • kinetic hydrate inhibitor polymer preferably is at most 90 °C. If the kinetic hydrate inhibitor polymer has a cloud point under actual
  • the operating temperature preferably is at most 60 °C, more specifically at most 50 °C. Sufficient cross-flow should be applied during operation to minimize build-up of polymeric contaminants.
  • a process into which the present invention can be incorporated is a process comprising
  • step (a) adding a kinetic hydrate inhibitor polymer having a molecular weight of at least 1000 Da to raw natural gas, (b) sending the mixture obtained in step (a) to a slug- catcher, and
  • step (c) separating the kinetic hydrate inhibitor polymer from at least part of the product of step (b) in a process according to the present invention.
  • the kinetic hydrate inhibitor polymer containing retentate obtained in step (c) can be added to raw natural gas either as such or after having been treated further .
  • the product of the slug catcher can be sent to a phase separator in which the mixture is separated into a hydrocarbonaceous gas, a liquid hydrocarbonaceous
  • step (c) only the bottom aqueous fraction is to be subjected to the process according to the present invention in step (c) .
  • the permeate obtained in step (c) preferably is subsequently subjected to condensate removal, water removal, separation of natural gas liquids and sulfur and carbon dioxide removal before being transported and/or liquefied .
  • Raw natural gas is gas as obtained from underground gas fields or extracted at the surface from the fluids produced from oil wells.
  • the temperature and pressure of the raw natural can vary widely.
  • the kinetic hydrate inhibitor polymer can be added to the raw natural gas in any way known to be suitable by someone skilled in the art.
  • the kinetic hydrate inhibitor is added as a solution as this
  • the slug catcher for use in step (b) is a vessel with sufficient buffer volume to store plugs of liquid, called slugs, which exit the pipeline.
  • the slug catcher feeds liquid at a lower rate to downstream processing units which prevents liquid overload of those units.
  • a phase separator which is optionally used for further treating the product of step (b) preferably is a three-phase separator comprising a normally horizontal vessel defining a liquid separation space and a gas space, which vessel has an inlet end space provided with a feed inlet and an outlet end space provided with separate outlets for the gaseous, the hydrocarbonaceous and the aqueous phase.
  • a preferred separator has been described in US patent specification 6537458.
  • Stripping involves treating the aqueous mixture with an inert gas such as clean natural gas or steam to remove gaseous hydrocarbons such as dissolved sour gases for example hydrogen sulphide. Steam is often used in a heated column. It has been found that stripping of the aqueous mixture can facilitate the membrane separation.
  • an inert gas such as clean natural gas or steam to remove gaseous hydrocarbons such as dissolved sour gases for example hydrogen sulphide. Steam is often used in a heated column. It has been found that stripping of the aqueous mixture can facilitate the membrane separation.
  • Another option is to treat the aqueous solution in the process according to the present invention and subsequently subject the permeate to stripping. This has the advantage that the kinetic hydrate inhibitor polymer will not interfere in the stripping column. Circumstances such as the line-up and kinetic hydrate inhibitor polymer applied, determine whether stripping is to be applied and if so, whether it is to be applied before or after the membrane treatment.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne un procédé de séparation de polymères inhibiteurs cinétiques d'hydrates ayant un poids moléculaire d'au moins 1000 Da d'un mélange aqueux comprenant en outre des hydrocarbures et des sels, ledit procédé consistant à mettre le mélange aqueux en contact avec le côté d'alimentation d'une membrane ayant un diamètre moyen des pores allant de 0,7 à 4 nm, et à obtenir du côté perméat de la membrane un perméat aqueux dont la concentration du polymère inhibiteur cinétique d'hydrates est au plus de 20 % de celle du mélange aqueux.
EP11761076.6A 2010-09-27 2011-09-23 Procédé de séparation de polymères inhibiteurs cinétiques d'hydrates Withdrawn EP2622041A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11761076.6A EP2622041A1 (fr) 2010-09-27 2011-09-23 Procédé de séparation de polymères inhibiteurs cinétiques d'hydrates

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10180196 2010-09-27
EP11761076.6A EP2622041A1 (fr) 2010-09-27 2011-09-23 Procédé de séparation de polymères inhibiteurs cinétiques d'hydrates
PCT/EP2011/066612 WO2012041785A1 (fr) 2010-09-27 2011-09-23 Procédé de séparation de polymères inhibiteurs cinétiques d'hydrates

Publications (1)

Publication Number Publication Date
EP2622041A1 true EP2622041A1 (fr) 2013-08-07

Family

ID=44677894

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11761076.6A Withdrawn EP2622041A1 (fr) 2010-09-27 2011-09-23 Procédé de séparation de polymères inhibiteurs cinétiques d'hydrates

Country Status (5)

Country Link
US (1) US20140144810A1 (fr)
EP (1) EP2622041A1 (fr)
AU (1) AU2011310681A1 (fr)
RU (1) RU2013119654A (fr)
WO (1) WO2012041785A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130087502A1 (en) * 2011-10-06 2013-04-11 Conocophillips Company Water impurity removal methods and systems
US10407611B2 (en) 2016-01-08 2019-09-10 Ecolab Usa Inc. Heavy oil rheology modifiers for flow improvement during production and transportation operations

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4519815A (en) * 1983-12-15 1985-05-28 Texas Eastern Engineering Ltd. Slug-catching method and apparatus
US5600044A (en) * 1994-09-15 1997-02-04 Exxon Production Research Company Method for inhibiting hydrate formation
AU4287700A (en) 1999-03-05 2000-09-21 Shell Internationale Research Maatschappij B.V. Three-phase separator
CA2404784A1 (fr) 2000-04-07 2001-10-18 Shell Internationale Research Maatschappij B.V. Procede destine a inhiber l'obturation de conduits par des hydrates de gaz
MX2007000640A (es) * 2004-07-16 2007-03-30 California Inst Of Techn Tratamiento de agua mediante filtracion mejorada por dendrimero.
CN101040031B (zh) * 2004-10-11 2010-10-13 国际壳牌研究有限公司 从烃混合物中分离发色体和/或沥青类污染物的方法
CA2602384A1 (fr) 2005-04-07 2006-10-19 Exxonmobil Upstream Research Company Recuperation d'inhibiteur d'hydrate cinetique
FR2914684A1 (fr) * 2007-04-03 2008-10-10 Total Sa Procede de recyclage d'agents retardateurs de formation d'hydrates
BRPI1008862B1 (pt) * 2009-02-05 2019-10-15 Shell Internationale Research Maatschappij B.V. Sistema e método para recuperar hidrocarbonetos a partir de uma formação

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012041785A1 *

Also Published As

Publication number Publication date
WO2012041785A1 (fr) 2012-04-05
US20140144810A1 (en) 2014-05-29
RU2013119654A (ru) 2014-11-10
AU2011310681A1 (en) 2013-05-02

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