WO2006005084A1 - Treatment of hydrocarbons - Google Patents
Treatment of hydrocarbons Download PDFInfo
- Publication number
- WO2006005084A1 WO2006005084A1 PCT/ZA2005/000100 ZA2005000100W WO2006005084A1 WO 2006005084 A1 WO2006005084 A1 WO 2006005084A1 ZA 2005000100 W ZA2005000100 W ZA 2005000100W WO 2006005084 A1 WO2006005084 A1 WO 2006005084A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- metal
- fischer
- tropsch
- filterable
- oxygenates
- Prior art date
Links
- 238000011282 treatment Methods 0.000 title claims abstract description 14
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 9
- 229930195733 hydrocarbon Natural products 0.000 title claims description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 66
- 239000002184 metal Substances 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 21
- 239000011541 reaction mixture Substances 0.000 claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000003463 adsorbent Substances 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000004703 alkoxides Chemical class 0.000 claims description 7
- 150000007942 carboxylates Chemical class 0.000 claims description 7
- 238000010335 hydrothermal treatment Methods 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 238000005367 electrostatic precipitation Methods 0.000 claims description 2
- 238000005189 flocculation Methods 0.000 claims description 2
- 230000016615 flocculation Effects 0.000 claims description 2
- 238000005188 flotation Methods 0.000 claims description 2
- 230000033444 hydroxylation Effects 0.000 claims description 2
- 238000005805 hydroxylation reaction Methods 0.000 claims description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 abstract description 3
- 230000002745 absorbent Effects 0.000 abstract description 3
- 239000004411 aluminium Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 125000002524 organometallic group Chemical group 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000011819 refractory material Substances 0.000 description 3
- 229910002019 Aerosil® 380 Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- -1 aluminium carboxylates Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
-
- 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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
Definitions
- the invention relates to treatment of hydrocarbons to reduce deposit formation in process equipment.
- the inventors have identified an area for process optimization in processing of hydrocarbons.
- the inventors have identified an area for process optimization in the processing of F-T synthesis products by hydroconversion in general.
- F-T derived product streams contain oxygenates and to a certain extent metals and/or metal species.
- Ketones, aldehydes, alcohols, esters and carboxylic acids are the main constituents of the oxygenate fraction.
- Carboxylic acids and alcohols are able to form under appropriate conditions carboxylate and/or alkoxide complexes and/or metalloxanes with the metals and/or metal species present.
- These metal carboxylates and/or alkoxides and/or metalloxanes may form deposits in processing equipment and catalyst beds. Eventually the deposits in the catalyst beds may grow to such an extent that reactor shutdowns are inevitable.
- the identified problem may be summarized as the plugging of downstream processing catalyst beds or bed by a constituent of said product streams or a reaction product of a constituent of said product streams.
- the organometallic material is likely to be rich in aluminium, and/or silicon, and/or titanium, and/or zirconium, and/or cobalt, and/or iron, and/or alkaline earth elements such as calcium and barium etc.
- metal oxygenate species that contribute to bed plugging and either one or both may be important:
- Fine particulates for example, fine particulates of less than 1 micron in diameter which can be stabilized by surface-active compounds (such as the oxygenates) allowing them to remain in suspension. However, when this surface layer is disrupted, the particulates precipitate and form deposits on collector media.
- surface-active compounds such as the oxygenates
- Organometallic type compounds for example, in the case of aluminium as the metal source, the formation of organoaluminium compounds of the Al-O-R type, like alkoxy-aluminium, aluminium carboxylates and alumoxanes, or of the Al-R type, like alkyl-aluminium, or combinations thereof are possible.
- Bed plugging has been seen with various catalysts and it occurs as a localized plug or as distributed particulate matter.
- the F-T synthesis product stream carries organometallic material and/or solubilized fine catalyst particulates and/or filter aid and/or refractory material and/or chemically leached metals from the reactor system in low concentrations.
- the wax contains oxygenates like acids and alcohols that help to keep the fine particulates in solubilized form in the wax.
- a method of treatment of a Fischer-Tropsch (F-T) reaction mixture including: - (a) modification of metal oxygenate components in the F-T reaction mixture in a hydrothermal reaction zone at hydrothermal reaction conditions ;
- the hydrothermal reaction conditions may at least partially coincide with F-T reaction conditions.
- the hydrothermal reaction conditions may include a temperature of above 100°C, preferably between 120°C to 37O 0 C, and even as high a 400°C, typically 160 0 C to 250 0 C and a pressure of 1 to 100 bar, preferably 5 to 50 bar.
- the filterable adsorbent may be added into the hydrothermal reaction zone .
- the addition rate of the adsorbent may be determined by the amount of metal oxygenates in the F-T wax.
- the addition rate may vary from 0.01 to 10 wt % of the F-T catalyst present in the reactor.
- the hydrothermai reaction zone may be in a Fischer-Tropsch reactor in which synthesis gas is reacted in the presence of Fischer-Tropsch catalysts to produce Fischer-Tropsch hydrocarbons, oxygenates, and water.
- the hydrothermai reaction zone may be at least partially downstream of the F-T reactor, and typically close to or at Fischer-Tropsch reaction conditions.
- the F-T reaction mixture may include synthesis gas, Fischer-Tropsch hydrocarbons, oxygenates, water, and catalyst particles.
- Modification may involve hydrothermai treatment, which may result in hydroxylation and formation of metal hydroxides and/or metal oxyhydroxides and/or metalloxanes.
- the treatment stage may be followed by one or of the following treating stages:
- F-T derived hydrocarbons contain oxygenates and to a certain extent metals and/or metal species.
- Ketones, aldehydes, alcohols, esters and carboxylic acids are the main constituents of the oxygenate fraction.
- Carboxylic acids are able to form under appropriate conditions metal carboxylate complexes with the metal species present.
- Alcohols are able to form under appropriate conditions metal alkoxide complexes with the metal species present.
- the metal oxygenate may be a metal carboxylate, a metal alkoxide or a combination thereof or a metalloxane.
- the metal oxygenate may be a carboxy substituted metalloxane.
- the Fischer-Tropsch reaction conditions may include a temperature of above 160°C, preferably between 200°C to 280°C, and even as high as 400°C, typically 230°C to 24O 0 C and a pressure of 18 to 50 bar, preferably between 20 to 30 bar.
- the Fischer-Tropsch reaction conditions may include the presence of water.
- the filterable adsorbent may be silica, which leads to the adsorption of the modified metal oxygenates on the silica particles, which can subsequently be removed by filtration or other treating methods.
- the treatment may also be achieved by maintaining the F-T product stream under the temperature and pressure of the FT reaction conditions after a primary filtration zone for sufficient time to enable particle growth or adsorption onto a filterable particle i.e. the hydrothermal treatment may be carried out by maintaining the reactor conditions between primary and secondary filtration zones for sufficient time to allow for particle growth or adsorption onto a filterable particle. Sufficient time will be between 1 to 60 minutes, preferably between 1 to 30 minutes and more preferably between 5 to 10 minutes.
- Filter materials used in the filtration include clays, silica, silica-alumina, cellulose, activated carbons, sintered metals and material filters such as nylons and polycarbonates.
- the adsorbents and/or filterable particles include clays, silica, silica-alumina, cellulose, activated carbons, sintered metals, titania and material filters such as nylons and polycarbonates.
- Growing of filterable particulates may be influenced by thermal and/or hydrothermal treatment conditions, and optionally, on any chemical treatment conditions which, depending on the acid used as the chemical treatment agent as well as the process conditions, reversible or irreversible particle growth may be obtained that in turn influences the removal of the modified metal species by filtration.
- Reactor wax from a Low-Temperature F-T (LTFT) plant was analyzed and found to contain metal carboxylates (M x [ ⁇ 2CR]y), carboxy substituted metalloxanes
- Example 1 Hydrothermal treatment and addition of an adsorbent to the F-T reactor for the removal of metal oxygenates present in the wax
- hydrothermal treatment ex-situ the reactor of F-T wax which contains metal oxygenates, results in the formation of modified metal oxygenates, which given sufficient time for particle growth, can be filtered or adsorbed on filterable adsorbents such as silica.
- a novel approach is that all the steps involving the hydrothermal treatment of the wax for the modification of the metal oxygenates present and their adsorption on filterable particles can all take place in-situ the F-T reactor under the hydrothermal environment prevailing in the F-T reactor at the FT reaction conditions of 22 bar and 230 0 C.
- the particle size of the silica used was 5 microns and 3 wt % relative to the F-T catalyst was added to the reactor.
- the results obtained in terms of aluminium and cobalt content, after filtration and at different times after the addition of the silica are given in Table 1.
- Example 2 Adding a filterable particle/adsorbent under hydrothermal conditions to modify and adsorb modified metal oxygenates.
- the wax (200 g) containing soluble metal oxygenates was first melted in an oven at 140 0 C. To the melted wax was added 0.1-0.01 wt % Aerosil 380 (Degussa). The wax was then heated to 170 °C with stirring (200 rpm). Water (4 ml) was placed in a metal tube that was connected to the Parr reactor. After the desired temperature was reached, a sample was taken. Thereafter, the water was added to the reaction mixture and samples were taken at 5 and 10 minutes (Table 2) and passed through a 2.5 micron filter. The water modified the metal complex so that it could adsorb onto the filterable particle.
- Example 3 Adsorbing the modified metal oxygenate onto an adsorbent.
- contaminated wax was pumped at a set temperature through a 10 mm diameter tube containing adsorbent or filter material.
- the pressure listed is caused by the wax flow rate and adsorbent characteristics.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a method of treatment of a Fischer-Tropsch (F-T) reaction mixture, said method including:- (a) modification of metal oxygenate components in the F-T reaction mixture in a hydrothermal reaction zone at hydrothermal reaction conditions; (b) exposing the F-T reaction mixture in the hydrothermal reaction zone to a filterable absorbent to facilitate adsorption of the modified metal oxygenate components onto the filterable absorbent.
Description
METHOD OF TREATMENT OF FISCHER-TROPSCH HYDROCARBONS
Field of the Invention
The invention relates to treatment of hydrocarbons to reduce deposit formation in process equipment.
Background to the Invention
The inventors have identified an area for process optimization in processing of hydrocarbons. In particular, the inventors have identified an area for process optimization in the processing of F-T synthesis products by hydroconversion in general.
F-T derived product streams contain oxygenates and to a certain extent metals and/or metal species. Ketones, aldehydes, alcohols, esters and carboxylic acids are the main constituents of the oxygenate fraction. Carboxylic acids and alcohols are able to form under appropriate conditions carboxylate and/or alkoxide complexes and/or metalloxanes with the metals and/or metal species present. These metal carboxylates and/or alkoxides and/or metalloxanes may form deposits in processing equipment and catalyst beds. Eventually the deposits in the catalyst beds may grow to such an extent that reactor shutdowns are inevitable.
The identified problem may be summarized as the plugging of downstream processing catalyst beds or bed by a constituent of said product streams or a reaction product of a constituent of said product streams.
Summary of invention
Although not being bound by theory, the inventors believe that the plugging is being caused by organometallic material and/or fine particulates. The organometallic material is likely to be rich in aluminium, and/or silicon, and/or
titanium, and/or zirconium, and/or cobalt, and/or iron, and/or alkaline earth elements such as calcium and barium etc.
The synthesis products from the F-T process were analyzed and it was found that the condensate fraction is devoid of metal impurities (of the order of 1 ppm or less), but that the wax contains metal impurities (of the order of 10 - 100 ppm).
This indicates that the F-T process and/or filtration system and/or refractory materials and/or chemically leached metals or metal species may be the source of the metal impurities.
There are possibly two forms of metal oxygenate species that contribute to bed plugging and either one or both may be important:
a) Fine particulates, for example, fine particulates of less than 1 micron in diameter which can be stabilized by surface-active compounds (such as the oxygenates) allowing them to remain in suspension. However, when this surface layer is disrupted, the particulates precipitate and form deposits on collector media.
b) Organometallic type compounds: for example, in the case of aluminium as the metal source, the formation of organoaluminium compounds of the Al-O-R type, like alkoxy-aluminium, aluminium carboxylates and alumoxanes, or of the Al-R type, like alkyl-aluminium, or combinations thereof are possible.
Bed plugging has been seen with various catalysts and it occurs as a localized plug or as distributed particulate matter.
It is hypothesized that the F-T synthesis product stream carries organometallic material and/or solubilized fine catalyst particulates and/or filter aid and/or refractory material and/or chemically leached metals from the reactor system in
low concentrations. The wax contains oxygenates like acids and alcohols that help to keep the fine particulates in solubilized form in the wax.
During hydroconversion, it is believed that these oxygenates that keep the particulates in suspension, and/or the ligands of the organometallic components, are hydrogenated and/or protonated and the modified metal species are then deposited on the hydroconversion reactor catalyst bed, leading to what is called "bed plugging".
Thus the inventors, after deliberation and experimentation, propose the following solution which may at least partially alleviate the above described problem.
According to a first aspect of the invention, there is provided a method of treatment of a Fischer-Tropsch (F-T) reaction mixture, said method including: - (a) modification of metal oxygenate components in the F-T reaction mixture in a hydrothermal reaction zone at hydrothermal reaction conditions ;
- (b) exposing the F-T reaction mixture in the hydrothermal reaction zone to a filterable adsorbent to facilitate adsorption of the modified metal oxygenate components onto the filterable adsorbent.
The hydrothermal reaction conditions may at least partially coincide with F-T reaction conditions.
The hydrothermal reaction conditions may include a temperature of above 100°C, preferably between 120°C to 37O0C, and even as high a 400°C, typically 1600C to 2500C and a pressure of 1 to 100 bar, preferably 5 to 50 bar.
The filterable adsorbent may be added into the hydrothermal reaction zone .
The addition rate of the adsorbent may be determined by the amount of metal
oxygenates in the F-T wax. The addition rate may vary from 0.01 to 10 wt % of the F-T catalyst present in the reactor.
The hydrothermai reaction zone may be in a Fischer-Tropsch reactor in which synthesis gas is reacted in the presence of Fischer-Tropsch catalysts to produce Fischer-Tropsch hydrocarbons, oxygenates, and water. However, the hydrothermai reaction zone may be at least partially downstream of the F-T reactor, and typically close to or at Fischer-Tropsch reaction conditions.
The F-T reaction mixture may include synthesis gas, Fischer-Tropsch hydrocarbons, oxygenates, water, and catalyst particles.
Modification may involve hydrothermai treatment, which may result in hydroxylation and formation of metal hydroxides and/or metal oxyhydroxides and/or metalloxanes.
The treatment stage may be followed by one or of the following treating stages:
(i) extracting the modified metal oxygenates with the aid of polar solvents;
(ii) filtering the modified metal oxygenates after sufficient time has been allowed for particle growth and/or adsorption onto a filterable particle;
adsorbing the modified metal oxygenate onto an adsorbent;
(iv) settling of the adsorbed metal oxygenates after sufficient time has been allowed for particle growth;
(v) by centrifuging out the modified metal oxygenates after sufficient time has been allowed for particle growth;
(vi) flocculation of the modified metal oxygenates;
(vii) magnetic precipitation;
(viii) electrostatic precipitation/settling; and
(ix) flotation of the modified metal oxygenates and fine particulates; or
(x) any combination of one or more of the above treatments
F-T derived hydrocarbons contain oxygenates and to a certain extent metals and/or metal species.
Ketones, aldehydes, alcohols, esters and carboxylic acids are the main constituents of the oxygenate fraction.
Carboxylic acids are able to form under appropriate conditions metal carboxylate complexes with the metal species present.
Alcohols are able to form under appropriate conditions metal alkoxide complexes with the metal species present.
The metal oxygenate may be a metal carboxylate, a metal alkoxide or a combination thereof or a metalloxane.
The metal oxygenate may be a carboxy substituted metalloxane.
The Fischer-Tropsch reaction conditions may include a temperature of above 160°C, preferably between 200°C to 280°C, and even as high as 400°C, typically
230°C to 24O0C and a pressure of 18 to 50 bar, preferably between 20 to 30 bar.
The Fischer-Tropsch reaction conditions may include the presence of water.
The filterable adsorbent may be silica, which leads to the adsorption of the modified metal oxygenates on the silica particles, which can subsequently be removed by filtration or other treating methods.
The treatment may also be achieved by maintaining the F-T product stream under the temperature and pressure of the FT reaction conditions after a primary filtration zone for sufficient time to enable particle growth or adsorption onto a filterable particle i.e. the hydrothermal treatment may be carried out by maintaining the reactor conditions between primary and secondary filtration zones for sufficient time to allow for particle growth or adsorption onto a filterable particle. Sufficient time will be between 1 to 60 minutes, preferably between 1 to 30 minutes and more preferably between 5 to 10 minutes.
Filter materials used in the filtration include clays, silica, silica-alumina, cellulose, activated carbons, sintered metals and material filters such as nylons and polycarbonates.
The adsorbents and/or filterable particles include clays, silica, silica-alumina, cellulose, activated carbons, sintered metals, titania and material filters such as nylons and polycarbonates.
Growing of filterable particulates may be influenced by thermal and/or hydrothermal treatment conditions, and optionally, on any chemical treatment conditions which, depending on the acid used as the chemical treatment agent as well as the process conditions, reversible or irreversible particle growth may be obtained that in turn influences the removal of the modified metal species by
filtration.
Examples of Employing the Method of the Invention
Reactor wax from a Low-Temperature F-T (LTFT) plant was analyzed and found to contain metal carboxylates (Mx[θ2CR]y), carboxy substituted metalloxanes
([M(O)x(OH)y(θ2CR)z]n), alkoxides and combinations thereof that were leached from the catalyst, and/or support, and/or reactor, and/or filter clays and/or refractory materials .
The longer the hydrocarbon chain (-CR) of the carboxylate or alkoxide ligands attached to the metal, the more soluble is the component in the wax.
Example 1. Hydrothermal treatment and addition of an adsorbent to the F-T reactor for the removal of metal oxygenates present in the wax
As was shown in examples elsewhere, hydrothermal treatment ex-situ the reactor of F-T wax, which contains metal oxygenates, results in the formation of modified metal oxygenates, which given sufficient time for particle growth, can be filtered or adsorbed on filterable adsorbents such as silica.
A novel approach is that all the steps involving the hydrothermal treatment of the wax for the modification of the metal oxygenates present and their adsorption on filterable particles can all take place in-situ the F-T reactor under the hydrothermal environment prevailing in the F-T reactor at the FT reaction conditions of 22 bar and 2300C.
The particle size of the silica used was 5 microns and 3 wt % relative to the F-T catalyst was added to the reactor. The results obtained in terms of aluminium and cobalt content, after filtration and at different times after the addition of the silica are given in Table 1.
Table 1: Aluminium and Cobalt Content of Wax
Example 2: Adding a filterable particle/adsorbent under hydrothermal conditions to modify and adsorb modified metal oxygenates.
The wax (200 g) containing soluble metal oxygenates was first melted in an oven at 140 0C. To the melted wax was added 0.1-0.01 wt % Aerosil 380 (Degussa). The wax was then heated to 170 °C with stirring (200 rpm). Water (4 ml) was placed in a metal tube that was connected to the Parr reactor. After the desired temperature was reached, a sample was taken. Thereafter, the water was added to the reaction mixture and samples were taken at 5 and 10 minutes (Table 2) and passed through a 2.5 micron filter. The water modified the metal complex so that it could adsorb onto the filterable particle.
Table 2: Adsorbent Addition
ppm of wt % silica Time Al % AI
Al in added (min) (ppm) removal starting wax
45 0.1 5 1 98
10 <1 >98
27 0.05 5 3 91
10 <1 >98
66 0.01 5 25 62
10 22 67
Example 3: Adsorbing the modified metal oxygenate onto an adsorbent.
In these experiments, contaminated wax was pumped at a set temperature through a 10 mm diameter tube containing adsorbent or filter material. The pressure listed is caused by the wax flow rate and adsorbent characteristics.
In these experiments, contaminated wax containing 22 ppm aluminium and other metals such as cobalt, was pumped through a spray dried Degussa silica (Aerosil 380) as filter/absorbent with water been added (see table 3). Almost complete removal of the aluminium was achieved.
F536 GCC Rev 2 Sasol
Claims
1. A method of treatment of a Fischer-Tropsch (F-T) reaction mixture, said method including:
(a) modification of metal oxygenate components in the F-T reaction mixture in a hydrothermal reaction zone at hydrothermal reaction conditions ;
(b) exposing the F-T reaction mixture in the hydrothermal reaction zone to a filterable adsorbent to facilitate adsorption of the modified metal oxygenate components onto the filterable adsorbent.
2. A method as claimed claim 1 , wherein the hydrothermal reaction conditions at least partially coincides with F-T reaction conditions.
3. A method as claimed in claim 1 or claim 2, wherein the hydrothermal reaction is carried out at a temperature of above 1000C.
4. A method as claimed in claim 3, wherein the hydrothermal reaction is carried out at a temperature of between 1200C to 370°C.
5. A method as claimed in claim 3, wherein the hydrothermal reaction is carried out at a temperature of as high as 400°C
6. A method as claimed in claim 3, wherein the hydrothermal reaction is carried out at a temperature of between 160°C to 2500C.
7. A method as claimed in any one of the preceding claims, wherein the filterable adsorbent is added into the hydrothermal reaction zone.
8. A method as claimed in claim 7, wherein the addition rate of the adsorbent is determined by the amount of metal oxygenates in the F-T wax.
9. A method as claimed in claim 8, wherein the addition rate varies from 0.01 to 10 wt % of the F-T catalyst present in the reactor.
10. A method as claimed in any one of the preceding claims 2 to 9, wherein the hydrothermal reaction zone is in a Fischer-Tropsch reactor in which synthesis gas is reacted in the presence of Fischer-Tropsch catalysts to produce Fischer- Tropsch hydrocarbons, oxygenates, and water.
11. A method as claimed in any one of the preceding claims 2 to 10, wherein the hydrothermal reaction zone is at least partially downstream of a Fischer- Tropsch reactor but close to or at Fischer-Tropsch reaction conditions.
12. A method as claimed in any one of the preceding claims, wherein modification involves hydrothermal treatment, which results in hydroxylation and formation of one or more of metal hydroxides, metal oxyhydroxides, and metalloxanes.
13. A method as claimed in any one of the preceding claims, wherein the treatment stage is followed by one or of the following treating stages:
i) extracting the modified metal oxygenates with the aid of polar solvents;
ii) filtering the modified metal oxygenates after sufficient time has been allowed for particle growth and/or adsorption onto a filterable particle;
iii) adsorbing the modified metal oxygenate onto an adsorbent; iv) settling of the adsorbed metal oxygenates after sufficient time has been allowed for particle growth;
v) by centrifuging out the modified metal oxygenates after sufficient time has been allowed for particle growth;
vi) flocculation of the modified metal oxygenates;
vii) magnetic precipitation;
viii) electrostatic precipitation/settling; and
ix) flotation of the modified metal oxygenates and fine particulates; or any combination of one or more of the above treatments
14. A method as claimed in any one of the preceding claims, wherein the metal oxygenate is selected from the group including at least a metal carboxylate, a metal alkoxide, a carboxy substituted metalloxane, and a combination thereof.
15. A method as claimed in any one of the preceding claims 2 to 14, wherein the Fischer-Tropsch reaction conditions includes a temperature of between 180°C and 400°C.
16. A method as claimed in claim 15, wherein the Fischer-Tropsch reaction conditions includes a temperature of 230°C to 240°C .
17. A method as claimed in any one of the preceding claims, wherein water is present in the Fischer-Tropsch reaction mixture.
18. A method as claimed in any one of the preceding claims, wherein the filterable adsorbent is selected from the group including at least silica, which leads to the adsorption of the modified metal oxygenates on the silica particles, which can subsequently be removed by filtration or other treating methods.
19. A method as claimed in any one of the preceding claims, including maintaining the F-T product stream under hydrothermal reaction conditions after a primary filtration zone for sufficient time to enable particle growth or adsorption onto a filterable particle.
20. A method as claimed in claim 19, including hydrothermal treatment carried out by maintaining the Fisher-Tropsch reaction conditions between primary and secondary filtration zones for sufficient time to allow for particle growth or adsorption onto a filterable particle.
21. A method as claimed in any one of claims 13 to 20, wherein one or more of the filter materials, adsorbents, and filterable particles used in the filtration are selected from the group including clays, silica, silica-alumina, cellulose, activated carbons, sintered metals, material filters, and combinations thereof.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2005260788A AU2005260788B2 (en) | 2004-07-06 | 2005-07-04 | Treatment of hydrocarbons |
| BRPI0512755A BRPI0512755B1 (en) | 2004-07-06 | 2005-07-04 | FISCHER-TROPSCH HYDROCARBON TREATMENT METHOD |
| GB0625234A GB2430442B (en) | 2004-07-06 | 2005-07-04 | Method of treatment of Fischer-Tropsch hydrocarbons |
| NO20070043A NO343004B1 (en) | 2004-07-06 | 2007-01-03 | Process for the treatment of Fischer-Tropsch hydrocarbons |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ZA2004/5363 | 2004-07-06 | ||
| ZA200405363 | 2004-07-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2006005084A1 true WO2006005084A1 (en) | 2006-01-12 |
Family
ID=35385367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/ZA2005/000100 WO2006005084A1 (en) | 2004-07-06 | 2005-07-04 | Treatment of hydrocarbons |
Country Status (7)
| Country | Link |
|---|---|
| AU (1) | AU2005260788B2 (en) |
| BR (1) | BRPI0512755B1 (en) |
| GB (1) | GB2430442B (en) |
| NO (1) | NO343004B1 (en) |
| RU (1) | RU2364615C2 (en) |
| WO (1) | WO2006005084A1 (en) |
| ZA (1) | ZA200610735B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010112690A1 (en) | 2009-04-03 | 2010-10-07 | IFP Energies Nouvelles | Method for the production of middle distillates, comprising the hydroisomerisation and hydrocracking of a heavy fraction originating from a fischer-tropsch effluent |
| WO2010112691A1 (en) | 2009-04-03 | 2010-10-07 | IFP Energies Nouvelles | Method for the production of middle distillates, comprising the hydroisomerisation and hydrocracking of a heavy fraction originating from a fischer-tropsch effluent using a resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2531324A (en) * | 1947-10-18 | 1950-11-21 | California Research Corp | Preparation of alkylated aromatic hydrocarbons and sulfonation thereof |
| WO2002007883A2 (en) * | 2000-07-24 | 2002-01-31 | Sasol Technology (Proprietary) Limited | Production of hydrocarbons from a synthesis gas |
| WO2003012008A2 (en) * | 2001-07-27 | 2003-02-13 | Sasol Technology (Proprietary) Limited | Production of fischer-tropsch synthesis produced wax |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2661362A (en) * | 1947-11-26 | 1953-12-01 | Standard Oil Dev Co | Removal of oxygenated organic compounds from hydrocarbons |
| RU2181747C1 (en) * | 2000-12-25 | 2002-04-27 | Новицкая Людмила Алексеевна | Method of production of liquid hydrocarbon products from carbon dioxide |
-
2005
- 2005-07-04 AU AU2005260788A patent/AU2005260788B2/en not_active Ceased
- 2005-07-04 BR BRPI0512755A patent/BRPI0512755B1/en not_active IP Right Cessation
- 2005-07-04 WO PCT/ZA2005/000100 patent/WO2006005084A1/en active Search and Examination
- 2005-07-04 GB GB0625234A patent/GB2430442B/en not_active Expired - Fee Related
- 2005-07-04 RU RU2007101687/04A patent/RU2364615C2/en active
-
2006
- 2006-12-20 ZA ZA200610735A patent/ZA200610735B/en unknown
-
2007
- 2007-01-03 NO NO20070043A patent/NO343004B1/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2531324A (en) * | 1947-10-18 | 1950-11-21 | California Research Corp | Preparation of alkylated aromatic hydrocarbons and sulfonation thereof |
| WO2002007883A2 (en) * | 2000-07-24 | 2002-01-31 | Sasol Technology (Proprietary) Limited | Production of hydrocarbons from a synthesis gas |
| WO2003012008A2 (en) * | 2001-07-27 | 2003-02-13 | Sasol Technology (Proprietary) Limited | Production of fischer-tropsch synthesis produced wax |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010112690A1 (en) | 2009-04-03 | 2010-10-07 | IFP Energies Nouvelles | Method for the production of middle distillates, comprising the hydroisomerisation and hydrocracking of a heavy fraction originating from a fischer-tropsch effluent |
| WO2010112691A1 (en) | 2009-04-03 | 2010-10-07 | IFP Energies Nouvelles | Method for the production of middle distillates, comprising the hydroisomerisation and hydrocracking of a heavy fraction originating from a fischer-tropsch effluent using a resin |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2430442B (en) | 2009-04-15 |
| GB0625234D0 (en) | 2007-02-07 |
| AU2005260788A1 (en) | 2006-01-12 |
| GB2430442A (en) | 2007-03-28 |
| BRPI0512755B1 (en) | 2015-10-06 |
| ZA200610735B (en) | 2008-06-25 |
| NO20070043L (en) | 2007-03-23 |
| NO343004B1 (en) | 2018-09-24 |
| BRPI0512755A (en) | 2008-04-08 |
| RU2364615C2 (en) | 2009-08-20 |
| AU2005260788B2 (en) | 2010-07-01 |
| RU2007101687A (en) | 2008-08-20 |
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