CA2125513A1 - Method of treating sour gas and liquid hydrocarbon streams - Google Patents
Method of treating sour gas and liquid hydrocarbon streamsInfo
- Publication number
- CA2125513A1 CA2125513A1 CA 2125513 CA2125513A CA2125513A1 CA 2125513 A1 CA2125513 A1 CA 2125513A1 CA 2125513 CA2125513 CA 2125513 CA 2125513 A CA2125513 A CA 2125513A CA 2125513 A1 CA2125513 A1 CA 2125513A1
- Authority
- CA
- Canada
- Prior art keywords
- stream
- triazine
- gas
- compound
- formaldehyde
- 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.)
- Abandoned
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
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/20—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
Abstract
ABSTRACT OF THE DISCLOSURE
Gas and liquid hydrocarbon streams are treated with a scavenging compound comprising a 1,3,5 trimethyl-hexahydro-1,3,5 triazine, prepared by the reaction of methylamine and formaldehyde. The triazine is substantially free of formaldehyde.
Gas and liquid hydrocarbon streams are treated with a scavenging compound comprising a 1,3,5 trimethyl-hexahydro-1,3,5 triazine, prepared by the reaction of methylamine and formaldehyde. The triazine is substantially free of formaldehyde.
Description
-` 211 25~
METHOD OF TREATING SOUR GAS
AND LIQUID HYDROCARBON STREAMS
CASE NO: ~XXON 40 BACKGROUNp OF THE INVENTION
This invention relates generally to the treatment of sour gas and liquid hydrocarbon streams to remove or reduce the levels of hydrogen sulfide therein. In one aspect, the invention relates to the treatment of sour gas and oil streams flowing in a flow line. In another aspect, the invention relates to kh~ use of nonregenerative scavengers to reduce the levels of hydrogen sulfide in natural gas and liquid hydro-carbon streams.
The toxicity o~ hydrogen sulfide in hydrocarbon streams is well known in the industry and considerable expense and efforts are PxpPnded annually to reduce its content to a safe level. Many regulations require pipeline gas to contain no more than 4 ppm hydrogen sulfide.
In large production facilities, it is generally more economical to install a reganerative system for treating sour gas streams. These systems typically employ a compound used in an absorption tower to contact the produced flu:ids and selectively absorb the hydrogen sulfide and possibly other toxic materials such as carbon dioxide and mercaptans. The absorption compound is then r~genera~ed and reused in the ~ystem. 'rypical hydrogen sul~ide absorption materials include alkanolamines, PEG, hindered amines, and the like.
.
- ' ' ' 2~2~3 ::
However, during a development stage of a field or in small producing fields where regenerative systems are not economical, it is necessary to treat the sour hydrocarbon production with nonregenerative scavengers.
Based on an article appearing in the OiI & Gas JournaI, January 30, 1989, nonregenerative scavengers for small plant hydrogen sulfide removal ~all into four groups: aldehyde based, metallic oxide based, caustic based, and other pro-cesses. In the removal of hydrogen su:Lfide by nonregene-rative compounds, the scavenger reacts with the hydrogen sulfide to form a nontoxic compound or a compound which can be removed from the hydrocarbon. For example, in the formal-dehyde type reaction, the reaction produces a chemical complex known as formthionals (e.g., trithiane).
As described in detail below, the present invention employs a nonregenera~ive scavenger which may be of the aldehyde type. These include low molecular weight aldehydes and ketones and adducts thereof. The low molecular weight aldehydes may also be combined with an alXyl or alkanolamine as disclosed in U.S. Patent 4,748,011. Other aldehyde derived scavengers include the reaction product of low molecular weight alkanolamines and aldehydes disclosed in U.S. Patent 4,978,512.
SUMMARY OF THE INVENTION
In accordance with the method of the present invention, an H2S sour gas or liquid hydrocarbons arP treated with 1,3,5-- 2~2~5~3 ,~
trimethyl-hexahydro-1,3,5 triazine to reduce the level of H2S
and mercaptans therein. The 1,3,5-trime~hyl-hexahydro - 1,3,5 triazine may be represented by the following formula (FORMULA
I) CH3 ~ N N _ CH3 ~J
The triazine is prepared by reacting trimethyl amine with formaldehyde.
The method of the present invention involves adding the triazine scavenger described above to any gas or liquid hydro-carhon containing H2S and/or mercaptans in a sufficient quan-tity to effectively reduce the levels of reactive S therein.
The method may also be employed by passing the sour gas through an absorption containing a solution of the scavenger.
DESCRIPTIONQF THE PREFERRED hMBODIMENTS
The method of the present invention may be used in the treatment of sour gas and oil production streams, as well as in petroleum (e.g. crude oil and re~ined products) contained in storage tanks, vessels, pipelines. etc.
As mentioned above, the scavenging composition use~ul in the method of the present invention is 1,3,5-trimethyl-hexa-hydro-1,3,5-triazine. (For convenience, this compound will s:imply be re~ rred to as "triazine" unless otherwise indicated 212~
to distinguish between other triazines.) The triazine (Formula I) i5 prepared by the condensation reaction of a trimethylamine and formaldehyde:
METHOD OF TREATING SOUR GAS
AND LIQUID HYDROCARBON STREAMS
CASE NO: ~XXON 40 BACKGROUNp OF THE INVENTION
This invention relates generally to the treatment of sour gas and liquid hydrocarbon streams to remove or reduce the levels of hydrogen sulfide therein. In one aspect, the invention relates to the treatment of sour gas and oil streams flowing in a flow line. In another aspect, the invention relates to kh~ use of nonregenerative scavengers to reduce the levels of hydrogen sulfide in natural gas and liquid hydro-carbon streams.
The toxicity o~ hydrogen sulfide in hydrocarbon streams is well known in the industry and considerable expense and efforts are PxpPnded annually to reduce its content to a safe level. Many regulations require pipeline gas to contain no more than 4 ppm hydrogen sulfide.
In large production facilities, it is generally more economical to install a reganerative system for treating sour gas streams. These systems typically employ a compound used in an absorption tower to contact the produced flu:ids and selectively absorb the hydrogen sulfide and possibly other toxic materials such as carbon dioxide and mercaptans. The absorption compound is then r~genera~ed and reused in the ~ystem. 'rypical hydrogen sul~ide absorption materials include alkanolamines, PEG, hindered amines, and the like.
.
- ' ' ' 2~2~3 ::
However, during a development stage of a field or in small producing fields where regenerative systems are not economical, it is necessary to treat the sour hydrocarbon production with nonregenerative scavengers.
Based on an article appearing in the OiI & Gas JournaI, January 30, 1989, nonregenerative scavengers for small plant hydrogen sulfide removal ~all into four groups: aldehyde based, metallic oxide based, caustic based, and other pro-cesses. In the removal of hydrogen su:Lfide by nonregene-rative compounds, the scavenger reacts with the hydrogen sulfide to form a nontoxic compound or a compound which can be removed from the hydrocarbon. For example, in the formal-dehyde type reaction, the reaction produces a chemical complex known as formthionals (e.g., trithiane).
As described in detail below, the present invention employs a nonregenera~ive scavenger which may be of the aldehyde type. These include low molecular weight aldehydes and ketones and adducts thereof. The low molecular weight aldehydes may also be combined with an alXyl or alkanolamine as disclosed in U.S. Patent 4,748,011. Other aldehyde derived scavengers include the reaction product of low molecular weight alkanolamines and aldehydes disclosed in U.S. Patent 4,978,512.
SUMMARY OF THE INVENTION
In accordance with the method of the present invention, an H2S sour gas or liquid hydrocarbons arP treated with 1,3,5-- 2~2~5~3 ,~
trimethyl-hexahydro-1,3,5 triazine to reduce the level of H2S
and mercaptans therein. The 1,3,5-trime~hyl-hexahydro - 1,3,5 triazine may be represented by the following formula (FORMULA
I) CH3 ~ N N _ CH3 ~J
The triazine is prepared by reacting trimethyl amine with formaldehyde.
The method of the present invention involves adding the triazine scavenger described above to any gas or liquid hydro-carhon containing H2S and/or mercaptans in a sufficient quan-tity to effectively reduce the levels of reactive S therein.
The method may also be employed by passing the sour gas through an absorption containing a solution of the scavenger.
DESCRIPTIONQF THE PREFERRED hMBODIMENTS
The method of the present invention may be used in the treatment of sour gas and oil production streams, as well as in petroleum (e.g. crude oil and re~ined products) contained in storage tanks, vessels, pipelines. etc.
As mentioned above, the scavenging composition use~ul in the method of the present invention is 1,3,5-trimethyl-hexa-hydro-1,3,5-triazine. (For convenience, this compound will s:imply be re~ rred to as "triazine" unless otherwise indicated 212~
to distinguish between other triazines.) The triazine (Formula I) i5 prepared by the condensation reaction of a trimethylamine and formaldehyde:
3 C~I3NH2 ~ 3CHzO C~3 N N - CH3 The ~ormaldehyde may be in the ~orm of formalin or para-formaldehyde~ with the ~ormer being preferred.
Other compounds such as hydrocarbon solvents may be present in the final product. These include xylenes, aromatic naphtha and alcohols.
In carrying out the reaction, an aqueous solution of methylamine is added slowly to a concentrated aqueous methanol-free solution of formaldehyde and the stoichiometry is maintained so that there is a slight excess of methylaminP
at the end of the reaction, maintaining a molar ratio of at least 1.01 ~e.g. about 1.02 moles3 o~ methylamine to 1.00 moles of formaldehyde for the overall process. Free formalde-hyde is minimized to <1000 ppm in the liquid. Slow addition is desirable to control the reaction t~mperature to below 1~0F. For climatization purposes, methanol or other solv~nts can be added back without ad~ersely affecting the fo~mclldehyde ~ 21~13 level. Thus, an essentially quantitative yield of 1,3,5-trimethyl-hexahydro-1,3,5-triazine can be formed under conditions which minimize the presence of objectionable amounts of free formaldehyde.
The triazine may also be manufactured by the reverse addition of formaldehyde to methylamine to produce the same result, provided the temperature is maintained below 105F to minimize methylamine loss by evaporation and provided the stoichiometry o~ the overall process is as described above.
The manufacture of the triazine by the method described above produces highly desirable scavengers for use in treat-ment o~ hydrocarbon streams because of the absence of formal-dehyde. The reasons for this are believed to be due to the following ~actors:
(1) The slight excess of methylamine drives the triazine formation to completion.
(2) Methylamine is a small molecule and ~trong base and as such does not require an additional base to form a stable triazine.
(3) The absence (or minimization) of methanol removes the possibility that formaldehyde is tied up as an acetal or hemiacetal of ~ormaldehy~e and methanol.
These materials, if present, would be competing with methylamine and hindering triazine formation.
Other compounds such as hydrocarbon solvents may be present in the final product. These include xylenes, aromatic naphtha and alcohols.
In carrying out the reaction, an aqueous solution of methylamine is added slowly to a concentrated aqueous methanol-free solution of formaldehyde and the stoichiometry is maintained so that there is a slight excess of methylaminP
at the end of the reaction, maintaining a molar ratio of at least 1.01 ~e.g. about 1.02 moles3 o~ methylamine to 1.00 moles of formaldehyde for the overall process. Free formalde-hyde is minimized to <1000 ppm in the liquid. Slow addition is desirable to control the reaction t~mperature to below 1~0F. For climatization purposes, methanol or other solv~nts can be added back without ad~ersely affecting the fo~mclldehyde ~ 21~13 level. Thus, an essentially quantitative yield of 1,3,5-trimethyl-hexahydro-1,3,5-triazine can be formed under conditions which minimize the presence of objectionable amounts of free formaldehyde.
The triazine may also be manufactured by the reverse addition of formaldehyde to methylamine to produce the same result, provided the temperature is maintained below 105F to minimize methylamine loss by evaporation and provided the stoichiometry o~ the overall process is as described above.
The manufacture of the triazine by the method described above produces highly desirable scavengers for use in treat-ment o~ hydrocarbon streams because of the absence of formal-dehyde. The reasons for this are believed to be due to the following ~actors:
(1) The slight excess of methylamine drives the triazine formation to completion.
(2) Methylamine is a small molecule and ~trong base and as such does not require an additional base to form a stable triazine.
(3) The absence (or minimization) of methanol removes the possibility that formaldehyde is tied up as an acetal or hemiacetal of ~ormaldehy~e and methanol.
These materials, if present, would be competing with methylamine and hindering triazine formation.
(4) Methylamine is a monofunctional primary amine unlike ethanolamine, which contains a hydroxy yxoup.
Methylamine cannot ~orm an oxazolidine, bis or 2~5~13 ~.
otherwise, thus clearly distinguishing the tri-methyl hexahydro triazina from the tri-(2 hydroxy-ethyl) hexahydro S triazines of the prior art.
The requirement to form such a structure as taught by U.S. Patent No. 4,978,572 is a 2-aminoalcohol such as monoethanol amine.
O~erations In carryiny out the method of the present in~ention, the scavenging composition is added to the gas or oil strPam in a concentration sufficient to substantially reduce the levels of H2S and/or mercaptans therein. ~n gas, generally from 0.01 to 0.12, preferably from 0.02 to 0.10, most preferably from 0.04 to 0.08 gallons of scavengPr product (34.5% active~ per MMSCF for each ppm of HzS removed will be sufficient for most applications. The treatment may also be based on weight of H2S in the gas. From .05 to 1.0, pre~erably 0.1 to .4 pounds of triazine per MMSCF per ppm H2S removed will normally be required.
In treating hydrocarbon streams, the scavenging compound contained in a solvent, such as water or alcohol, may be injected by conventional means such as a chemical injection pump or any other mechanical means ~or disp2rsing chemicals in the stream. The injection may be in the ~low lines or the gas may be pa~sed through an absorption tower containing a solution of the triazine.
212~13 ,~ .
For sour oil from .5 to 5 pounds, preerably from 1.0 to 4.0 pounds, and most preferably from 1.5 to 3.0 pounds of triazine per pound of H2S removed will be sufficient.
In addition to the triazines described above, the chemical formulations may also contain other compounds such as ethoxylated alcohols, ethoxylated phenols, sulfates of ethoxylated alcohols and phenols, quaternary amines, corrosion inhibitors, and the like. The preferred scavenger formulation comprlses 10-50 wt% actives (triazines).
The H2S scavenging ability of the 1,3,5-tri~methyl-hexahydro~1,3,5 triazine is believed to be due to its reaction with hydrogen sulfide to produce sulfur containing organic compounds such as dithiazines.
EXPERIMENTS
Field Test. Comparative tests were run on a commercial gas gathering system with gas flow through a 6" pipeline:
Gas Flow Rate - 6.5 ~MSCFD
H2S present - 250 ppm The scavengers used to treat the facility were as follows:
Formula I Product: 34.5 wt% 1,3,5-trimethyl-hexahydro-1,3,5 triazi~e tFormula I):
65.5 wt% solvent ~waker) Commerci~l Scavenger: 34.5 wt% 1,3,5-tri-(2-hydroxy-ethyl)-hexahydro-1,3,5-triazine.
65.5 wt% o~ a solvent.
.. ~ , , :
-- 212S~3 The treatment with the Commercial Scavenger involved con~
tinuous injection into the pipeline at a rate of 75 gallons per day, and a 55 gallon sllig treatment twice a week.
This treatment successfully maintained the H2S level in the gas at the 4 ppm limit, but experienced severe buildup of reaction by-products, requiring cleanout every other day.
The treatment with the Formula I Product involved injec-tion into the 6" pipeline at a rate of 73 gallons per day with no need for any slug treatments. The use of the Formula I
Product limited the H2S content of the gas to 4 ppm. In a four month treatment, only one cleanout was required.
Performance EfficiencY Tests Experiment 1: Side stream bubble tower tests were per-formed at a commercial facility to determine the absorption efficiency and capacity of the Formula I Product in the removal of hydrogen sulfide (H2S) from a natural gas stream.
The procedure was as follows: A 2-liter absorption column was used. Three milliliters of the Formula I Product were diluted in 500 milliliters of distilled water. The inlet concentration of H2S was determined, the cylinder ~as filled, and the flow rate of the natural gas stream was set at 3.0 liters of gas per minute. The flow rate was checked every 7 to 8 minutes and the outlet H2S concentration was determined every 15 minutes. The test was continued until the outlet H2S
concentration was near the inlet le~el. The results are pre-~ented in Table I.
2~25~3 :
TABLE I
Elap~ed H2S ~2S Liters H2S
Time Inlet OutletPa~sed R i~n~d ~Hours) (ppm) ~ppm)(in interval) (gram~) _ _ _ _ _ _ _ _ _ _ _ _ _ .
. oo 860 0 .25 8~0 0 45 .060 .50 860 5 45 059 .75 860 10 45 .059 1.00 950 45 45 .063 1.25 950 130 45 .057 1.50 950 220 45 .051 1.75 950 300 45 .04 2.00 950 350 45 .042 2.25 g50 400 ~5 .03 2.50 950 400 45 .038 2.75 950 700 ~5 o 017 The total H2S removed was 1.467 pounds per gallon of the Formula I Product (34.5% active).
Experiment 2: A second side stream bubble tower test was performed at a second commercial facility.
The procedure was as follows: A 2-liter absorption column was used. Fifty milliliters of Formula I Product were diluted in 400 milliliters of distilled water. The inlet concentration of H2S was determined, the cylinder was filled, and the flow rate was set at 3.0 litPrs of gas per minute.
The flow rate was checked every 10 minutes and the outlet H2S
concentration was determined every 15 minutes. ~he test w~s continued until the outlet H25 conrentration was approximately forty percent (40%) o~ the inlet level. The test results are presented in TABL~ II.
~:',: ' ' ' ':. ' 21% 3~ ~
TABLE II
Elapsed ~2S ~2S Liters H2S
Ti~e Inlet Outlet Pas~ed R3Knld (Hour~) (ppm) (ppm)(in inter~al)(gr~ms) _~_________._________________________________________________ ___________ .00 30000 0 0 .000 .25 30000 0 45 2.078 .50 30000 5 45 2.077 .75 30000 50 45 2.074 1.00 30000 7800 45 1.537 1.25 30000 8200 15 .503 1.50 30000 l0000 15 .462 1~75 30000 11800 15 420 Total: 9.152 The total H2S remoYed was 1.526 pounds/gallon of Formula I Product (34.5% active).
Com~arative Tests 1 and 2: A side stream hubble tower test was performed at the commercial facility tested in Experiment 2 to determine the a~sorption e~ficiency and capacity of the commercial scavenger used in the Field Test described abovP except the active triazine was between 45 and 50 wt%.
In one test procedure, a 2-lit~r absorption column was used. The cylinder was charged with 100 milliliters of the commercial scavenger and 500 milliliters of water. A gas 10w rate of 4.0 liters per minute was passed through the cylinder.
In the second test procedure, a 250 milliliter cylinder absorption column was used. The cylinder was charged with 100 milliliters of the commercial scavenger~ A gas flow rate o~ 1.0 to 1.5 liters per minute was passed throuyh the cylinder.
2 ~ 2 ~ ~ ~ 3 The inlet and e~fluent hydrogen sulfide (H2S) concen-trations were determined by Gastec tubes.
The test results for the two tests are presented in TABLES III and IV.
TABLE III
Elapsed H2S H2S
Time Inlet Outlet (~ours) (ppm) (ppm) Test Comments _____ __. __________________________________________________ .00 55000 0 Test Started .17 55000 0 Added 0.5 ml .25 55000 0 antifoam agent .50 55000 10 .75 55000 600 Ended Test A total of 1O15 pounds of H2S per gallon of the scavenger (45-50~ active) were removed.
TABLE IV
Elapsed ~2S H2S
Time Inlet Outlet (Hours) (ppm) (ppm) Test Comments _______.______________ ____________________________________ .oo 550000 Test Started .25 550000 Added lo0 ml .50 550000 antifoam "E-22"
.75 550000 1.00 550000 1.25 55000o 1.50 550000 1.75 5500010 2.00 55000100 2.25 550001200 A total of 1.22 pounds of H2S per gallon of the commer-cial scavenger (~5-50% active) were removed.
- : . . :
, ~ ~ ; ~ : : : :
:
2~S~ 3 Comparison of the Performance of Yormula _I and the Commercial Scavenqer: The composition of the Commercial Scavenger is 45.0% to 50.0% by weight of 1,3,5-tri(2-hydroxy-~thyl)-hexahydro-1,3,5-triazine and the Formula I Product is 34.4% by weight of 1,3,5-trimethyl-hexahydro-1,3,5-triazine.
The efficiency based on the weight of the actives ttriazines) in the 4 tests described above were as follows:
Pounds of H2S Removed per pound of Formula I - 0.514 Pounds of H2S Removed per pound of commercial scavenyer (actives~ - 0.27 Based on the average results, the Formula I treatments resulted in a 52% improvement over the commercial scavenger in removing H2S~
Solubility Tests: Laboratory tests have shown that the solubility characteristics of the reaction products of hydrogensulfidewithl,3,5-trimethyl-hexahydro-1,3,5-triazine are more soluble in hydrocarbon medium than the reaction products of hydrogen sulfide with 1,3,5-tri-(2-hydroxyethyl)-hexahydro-1,3,5-triazine. This is a highly desirable ~esult, because it reduces plugging or fouling by reaction products as demonstrated in the ~ield tests using the commercial scavenger.
Summary of ExPeriments: The above experiments demon-strate that the Formula I soavenger (1,3,5-tr;.methyl-hexahydro~l,3,5 triazine) resulted in imp:roved per~ormance ~: , : :
,., over the closest prior art scavenger (1,3,5(2-hydroxyethyl)-hexahydro-1,3,5 triazine), in terms of H2S removal.
In addition, the Formula I scavenger did not result in by-products that required frequent cleaning.
Also in addition, the manufacture and use of the scavenger in accordance with the present invention offers the advantage that it is ecologically acceptable since it is sub-stantially free of ~oxmaldehydes.
" ....,. ~,,:.-- ,, - -: : .
Methylamine cannot ~orm an oxazolidine, bis or 2~5~13 ~.
otherwise, thus clearly distinguishing the tri-methyl hexahydro triazina from the tri-(2 hydroxy-ethyl) hexahydro S triazines of the prior art.
The requirement to form such a structure as taught by U.S. Patent No. 4,978,572 is a 2-aminoalcohol such as monoethanol amine.
O~erations In carryiny out the method of the present in~ention, the scavenging composition is added to the gas or oil strPam in a concentration sufficient to substantially reduce the levels of H2S and/or mercaptans therein. ~n gas, generally from 0.01 to 0.12, preferably from 0.02 to 0.10, most preferably from 0.04 to 0.08 gallons of scavengPr product (34.5% active~ per MMSCF for each ppm of HzS removed will be sufficient for most applications. The treatment may also be based on weight of H2S in the gas. From .05 to 1.0, pre~erably 0.1 to .4 pounds of triazine per MMSCF per ppm H2S removed will normally be required.
In treating hydrocarbon streams, the scavenging compound contained in a solvent, such as water or alcohol, may be injected by conventional means such as a chemical injection pump or any other mechanical means ~or disp2rsing chemicals in the stream. The injection may be in the ~low lines or the gas may be pa~sed through an absorption tower containing a solution of the triazine.
212~13 ,~ .
For sour oil from .5 to 5 pounds, preerably from 1.0 to 4.0 pounds, and most preferably from 1.5 to 3.0 pounds of triazine per pound of H2S removed will be sufficient.
In addition to the triazines described above, the chemical formulations may also contain other compounds such as ethoxylated alcohols, ethoxylated phenols, sulfates of ethoxylated alcohols and phenols, quaternary amines, corrosion inhibitors, and the like. The preferred scavenger formulation comprlses 10-50 wt% actives (triazines).
The H2S scavenging ability of the 1,3,5-tri~methyl-hexahydro~1,3,5 triazine is believed to be due to its reaction with hydrogen sulfide to produce sulfur containing organic compounds such as dithiazines.
EXPERIMENTS
Field Test. Comparative tests were run on a commercial gas gathering system with gas flow through a 6" pipeline:
Gas Flow Rate - 6.5 ~MSCFD
H2S present - 250 ppm The scavengers used to treat the facility were as follows:
Formula I Product: 34.5 wt% 1,3,5-trimethyl-hexahydro-1,3,5 triazi~e tFormula I):
65.5 wt% solvent ~waker) Commerci~l Scavenger: 34.5 wt% 1,3,5-tri-(2-hydroxy-ethyl)-hexahydro-1,3,5-triazine.
65.5 wt% o~ a solvent.
.. ~ , , :
-- 212S~3 The treatment with the Commercial Scavenger involved con~
tinuous injection into the pipeline at a rate of 75 gallons per day, and a 55 gallon sllig treatment twice a week.
This treatment successfully maintained the H2S level in the gas at the 4 ppm limit, but experienced severe buildup of reaction by-products, requiring cleanout every other day.
The treatment with the Formula I Product involved injec-tion into the 6" pipeline at a rate of 73 gallons per day with no need for any slug treatments. The use of the Formula I
Product limited the H2S content of the gas to 4 ppm. In a four month treatment, only one cleanout was required.
Performance EfficiencY Tests Experiment 1: Side stream bubble tower tests were per-formed at a commercial facility to determine the absorption efficiency and capacity of the Formula I Product in the removal of hydrogen sulfide (H2S) from a natural gas stream.
The procedure was as follows: A 2-liter absorption column was used. Three milliliters of the Formula I Product were diluted in 500 milliliters of distilled water. The inlet concentration of H2S was determined, the cylinder ~as filled, and the flow rate of the natural gas stream was set at 3.0 liters of gas per minute. The flow rate was checked every 7 to 8 minutes and the outlet H2S concentration was determined every 15 minutes. The test was continued until the outlet H2S
concentration was near the inlet le~el. The results are pre-~ented in Table I.
2~25~3 :
TABLE I
Elap~ed H2S ~2S Liters H2S
Time Inlet OutletPa~sed R i~n~d ~Hours) (ppm) ~ppm)(in interval) (gram~) _ _ _ _ _ _ _ _ _ _ _ _ _ .
. oo 860 0 .25 8~0 0 45 .060 .50 860 5 45 059 .75 860 10 45 .059 1.00 950 45 45 .063 1.25 950 130 45 .057 1.50 950 220 45 .051 1.75 950 300 45 .04 2.00 950 350 45 .042 2.25 g50 400 ~5 .03 2.50 950 400 45 .038 2.75 950 700 ~5 o 017 The total H2S removed was 1.467 pounds per gallon of the Formula I Product (34.5% active).
Experiment 2: A second side stream bubble tower test was performed at a second commercial facility.
The procedure was as follows: A 2-liter absorption column was used. Fifty milliliters of Formula I Product were diluted in 400 milliliters of distilled water. The inlet concentration of H2S was determined, the cylinder was filled, and the flow rate was set at 3.0 litPrs of gas per minute.
The flow rate was checked every 10 minutes and the outlet H2S
concentration was determined every 15 minutes. ~he test w~s continued until the outlet H25 conrentration was approximately forty percent (40%) o~ the inlet level. The test results are presented in TABL~ II.
~:',: ' ' ' ':. ' 21% 3~ ~
TABLE II
Elapsed ~2S ~2S Liters H2S
Ti~e Inlet Outlet Pas~ed R3Knld (Hour~) (ppm) (ppm)(in inter~al)(gr~ms) _~_________._________________________________________________ ___________ .00 30000 0 0 .000 .25 30000 0 45 2.078 .50 30000 5 45 2.077 .75 30000 50 45 2.074 1.00 30000 7800 45 1.537 1.25 30000 8200 15 .503 1.50 30000 l0000 15 .462 1~75 30000 11800 15 420 Total: 9.152 The total H2S remoYed was 1.526 pounds/gallon of Formula I Product (34.5% active).
Com~arative Tests 1 and 2: A side stream hubble tower test was performed at the commercial facility tested in Experiment 2 to determine the a~sorption e~ficiency and capacity of the commercial scavenger used in the Field Test described abovP except the active triazine was between 45 and 50 wt%.
In one test procedure, a 2-lit~r absorption column was used. The cylinder was charged with 100 milliliters of the commercial scavenger and 500 milliliters of water. A gas 10w rate of 4.0 liters per minute was passed through the cylinder.
In the second test procedure, a 250 milliliter cylinder absorption column was used. The cylinder was charged with 100 milliliters of the commercial scavenger~ A gas flow rate o~ 1.0 to 1.5 liters per minute was passed throuyh the cylinder.
2 ~ 2 ~ ~ ~ 3 The inlet and e~fluent hydrogen sulfide (H2S) concen-trations were determined by Gastec tubes.
The test results for the two tests are presented in TABLES III and IV.
TABLE III
Elapsed H2S H2S
Time Inlet Outlet (~ours) (ppm) (ppm) Test Comments _____ __. __________________________________________________ .00 55000 0 Test Started .17 55000 0 Added 0.5 ml .25 55000 0 antifoam agent .50 55000 10 .75 55000 600 Ended Test A total of 1O15 pounds of H2S per gallon of the scavenger (45-50~ active) were removed.
TABLE IV
Elapsed ~2S H2S
Time Inlet Outlet (Hours) (ppm) (ppm) Test Comments _______.______________ ____________________________________ .oo 550000 Test Started .25 550000 Added lo0 ml .50 550000 antifoam "E-22"
.75 550000 1.00 550000 1.25 55000o 1.50 550000 1.75 5500010 2.00 55000100 2.25 550001200 A total of 1.22 pounds of H2S per gallon of the commer-cial scavenger (~5-50% active) were removed.
- : . . :
, ~ ~ ; ~ : : : :
:
2~S~ 3 Comparison of the Performance of Yormula _I and the Commercial Scavenqer: The composition of the Commercial Scavenger is 45.0% to 50.0% by weight of 1,3,5-tri(2-hydroxy-~thyl)-hexahydro-1,3,5-triazine and the Formula I Product is 34.4% by weight of 1,3,5-trimethyl-hexahydro-1,3,5-triazine.
The efficiency based on the weight of the actives ttriazines) in the 4 tests described above were as follows:
Pounds of H2S Removed per pound of Formula I - 0.514 Pounds of H2S Removed per pound of commercial scavenyer (actives~ - 0.27 Based on the average results, the Formula I treatments resulted in a 52% improvement over the commercial scavenger in removing H2S~
Solubility Tests: Laboratory tests have shown that the solubility characteristics of the reaction products of hydrogensulfidewithl,3,5-trimethyl-hexahydro-1,3,5-triazine are more soluble in hydrocarbon medium than the reaction products of hydrogen sulfide with 1,3,5-tri-(2-hydroxyethyl)-hexahydro-1,3,5-triazine. This is a highly desirable ~esult, because it reduces plugging or fouling by reaction products as demonstrated in the ~ield tests using the commercial scavenger.
Summary of ExPeriments: The above experiments demon-strate that the Formula I soavenger (1,3,5-tr;.methyl-hexahydro~l,3,5 triazine) resulted in imp:roved per~ormance ~: , : :
,., over the closest prior art scavenger (1,3,5(2-hydroxyethyl)-hexahydro-1,3,5 triazine), in terms of H2S removal.
In addition, the Formula I scavenger did not result in by-products that required frequent cleaning.
Also in addition, the manufacture and use of the scavenger in accordance with the present invention offers the advantage that it is ecologically acceptable since it is sub-stantially free of ~oxmaldehydes.
" ....,. ~,,:.-- ,, - -: : .
Claims (8)
1. A method of reducing H2S and mercaptans in a gas or liquid hydrocarbon stream or mixtures thereof which comprises contacting the stream with an effective amount of a compound capable of scavenging H2S or mercaptans, said compound com-prising 1,3,5-trimethyl-hexahydro-triazine which is the reaction product of methylamine and formaldehyde.
2. The method of claim 1 wherein the reaction product is substantially free of formaldehyde.
3. The method of claim 1 wherein the stream is a gas stream and the compound is injected into the stream to provide the stream with from 0.05 to 1.0 pounds of the triazine per MMSCF of the gas stream per ppm of the H2S removed.
4. The method of claim 1 wherein the stream is a liquid hydrocarbon stream and the compound is introduced therein in an amount equal to .5 to 5 pounds of triazine per pound of H2S
removed.
removed.
5. The method of claim 1 wherein the stream is a gas stream and is contacted with the compound by passing the stream through an absorption tower containing an aqueous solution of the compound.
6. The method of claim 1 wherein the reaction product results from reacting an aqueous solution of formaldehyde substantially free of methanol with an aqueous solution of methylamine.
7. A method of treating a gas or liquid hydrocarbon stream to remove H2S therefrom which comprises contacting the stream with a scavenging compound prepared by reacting an aqueous solution of methylamine with an aqueous solution of formaldehyde substantially free of methanol, wherein the mole ratio of the reactants is such to provide the reaction with an excess of the amine at the end of the reaction.
8. The method of claim 7 wherein the mole ratio of methylamine/formaldehyde at the end of the reaction is 1.01/
1.00 or above.
1.00 or above.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US100,132 | 1979-12-04 | ||
| US10013293A | 1993-07-30 | 1993-07-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2125513A1 true CA2125513A1 (en) | 1995-01-31 |
Family
ID=22278250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2125513 Abandoned CA2125513A1 (en) | 1993-07-30 | 1994-06-09 | Method of treating sour gas and liquid hydrocarbon streams |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0636675A3 (en) |
| CA (1) | CA2125513A1 (en) |
| NO (1) | NO942415L (en) |
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-
1994
- 1994-06-09 CA CA 2125513 patent/CA2125513A1/en not_active Abandoned
- 1994-06-24 NO NO942415A patent/NO942415L/en unknown
- 1994-07-15 EP EP94305225A patent/EP0636675A3/en not_active Withdrawn
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Also Published As
| Publication number | Publication date |
|---|---|
| NO942415D0 (en) | 1994-06-24 |
| NO942415L (en) | 1995-01-31 |
| EP0636675A3 (en) | 1995-04-19 |
| EP0636675A2 (en) | 1995-02-01 |
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