Use of renewable oil in hydrotreatment process

Abstract

The use of bio oil from at least one renewable source in a hydrotreatment process, in which process hydrocarbons are formed from said glyceride oil in a catalytic reaction, and the iron content of said bio oil is less than 1 w-ppm calculated as elemental iron. A bio oil intermediate including bio oil from at least one renewable source and the iron content of said bio oil is less than 1 w-ppm calculated as elemental iron.

Claims

1. A method of hydrotreating a feed stream of bio oil feedstock to be introduced to at least one catalyst bed of a hydrodeoxygenation reactor to form hydrocarbons for a renewable fuel, the method comprising: correlating a total cumulative feed containing a total cumulative iron content within a feed stream of bio oil feedstock, to an increase in pressure drop across the at least one catalyst bed representative of catalyst bed plugging; selecting a cumulative amount of iron to be introduced into the at least one catalyst bed of the hydrodeoxygenation reactor relative to an expected catalyst bed life cycle length to thereby avoid catalyst bed plugging; and introducing the feed stream of bio oil feedstock with iron content to the at least one catalyst bed of the hydrodeoxygenation reactor during a hydrotreatment process to form hydrocarbons without catalyst bed plugging.

2. The method of claim 1, comprising: pretreating the feed stream of bio oil feedstock to a selected iron concentration for introduction to the hydrodeoxygenation reactor so as not to shorten the expected catalyst bed cycle length due to catalyst bed plugging caused by an increase in pressure drop within the hydrodeoxygenation reactor.

3. The method of claim 1, wherein the iron concentration is selected as a function of dimensioning design of the hydrodeoxygenation reactor and wherein the method comprises: assessing the expected catalyst bed life cycle length based on catalyst deactivation.

4. The method of claim 1, wherein the bio oil feedstock contains phosphorous.

5. The method of claim 3, comprising: calculating the expected catalyst bed life cycle length based on catalyst deactivation by a feed stream of the bio oil feedstock.

6. The method of claim 1, wherein: the catalyst bed plugging in the reactor is represented as a pressure drop of 3 bar across the hydrodeoxygenation reactor relative to an initial pressure of 0.5 bar.

7. The method of claim 1, wherein: the catalyst bed plugging in the hydrodeoxygenation reactor is represented as a pressure drop of 2.5 bar.

8. The method of claim 1, wherein: a rate of catalyst bed plugging across the catalyst bed in the reactor is determined by dividing an increase in pressure drop across the catalyst bed at a given time with a total cumulative feed introduced in the hydrodeoxygenation reactor.

9. The method of claim 7, comprising: adding hydrogen to the bio oil feedstock.

10. The method of claim 1, wherein the bio oil feedstock contains: a concentration of phosphorous of less than 5 w-pp; and a total concentration of alkali metals and alkali earth metals of less than 1-w-ppm.

11. The method of claim 1, wherein the hydrodeoxygenation reactor comprises: a NiMo catalyst bed.

12. The method of claim 1, wherein the hydrodeoxygenation reactor comprises: a CoMo catalyst bed.

13. The method of claim 1, comprising: subjecting the formed hydrocarbons output from the hydrodeoxygenation reactor as n-paraffins to isomerization to form iso-paraffins.

14. The method of claim 10, wherein the bio oil feed stock contains: an iron concentration of less than 1 to 0.2 w-ppm calculated as elemental iron.

15. The method of claim 1, wherein the bio oil feed stock contains: an iron concentration of less than 1 to 0.2 w-ppm calculated as elemental iron.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows the pressure drop over the catalyst bed in relation to the cumulative feed, in accordance with an exemplary aspect.

(2) FIG. 2 shows the correlation between absolute increase in pressure drop and absolute masses of P and Fe found in the dust, in accordance with an exemplary aspect.

(3) FIG. 3 shows the correlation between rate of increase in pressure drop (in bar kg (feed) and concentrations of P and Fe in the feed, in accordance with an exemplary aspect.

DETAILED DESCRIPTION

(4) Disclosed is the use of bio oil from at least one renewable source, in a hydrotreatment process, in which process hydrocarbons are formed in a catalytic reaction and the iron content of the bio oil is less than 1 w-ppm, for example, less than 0.5 and, for example, less than 0.25 w-ppm calculated as elemental iron. The use of bio oil with extremely low content of iron can be employed to reduce or avoid plugging of the catalyst used in the hydrotreatment reaction.

(5) An exemplary embodiment relates to the use of a glyceride oil from at least one renewable source in a hydrotreatment process, in which process hydrocarbons are formed in a catalytic reaction and the iron content of the glyceride oil is less than 1 w-ppm, for example, less than 0.5 w-ppm and, for example, 0.25 w-ppm calculated as elemental iron.

(6) The hydrotreating catalyst was found to be plugged, for example, in large scale production over a certain time. The particles responsible for the plugging of the catalyst were found upon analysis to contain high amounts of phosphorous and metals. Further studies lead to the surprising finding that the iron content of the feed used in the hydrotreatment process is responsible for the plugging of the catalyst. An exemplary aspect therefore relates to renewable oil with very low iron content as the starting material for a hydrotreatment process.

(7) Renewable oil enables longer running time of hydrotreating catalysts without plugging. Previous studies have established that impurities such as phosphorous and Na, Ca and Mg metals present in the feedstock may be responsible for deactivation of the catalyst. An exemplary aspect can address the problem of catalyst plugging and ensure smooth running of the process and stable reaction conditions allowing manufacture of hydrocarbons from glyceride oil with high conversion rate and high selectivity.

(8) In addition, an exemplary aspect can prevent the hydrotreating catalyst from deactivation, or reduce the degree of deactivation, and the low amount of Fe in the oil minimises the oxidation of the renewable oil. Iron compounds can act as oxidants.

(9) Here, bio oil is understood to mean any oil originating from a renewable (bio) source, including, for example, vegetable, animal or microbial sources. Bio oils can comprise at least fatty acids or fatty acid derivatives such as glycerides, alkyl esters of fatty acids, fatty acid alcohols or soaps.

(10) Here, glyceride oil is understood to mean any oil which comprises triacylglycerides. The glyceride oil may also comprise di- and monoacylglycerides as well as fatty acids and their derivatives such as alkyl esters especially methyl esters. The chain length of the hydrocarbon chains in the glyceride oil can be from at least C8 up to C24. The term glyceride oil is meant to include at least, but not limited to rapeseed oil, colza oil canola oil, tall oil, sunflower oil, soybean oil, hempseed oil, cottonseed oil, corn oil, olive oil, linseed oil, mustard oil, palm oil, peanut oil, castor oil, coconut oil, camellia oil, jatropha oil, oils derived from microbial sources, which are possible genetically modified and includes at least algae, bacteria, moulds and filamentous fungi; animal fats, fish oil, lard, tallow, train oil, recycled fats from the food industry and any mixture of the oils.

(11) Here, oil from renewable source or renewable oil is understood to mean any oil originating from a source that can be considered renewable, i.e., not fossil. Renewable sources include at least all plant (vegetable) and animal based sources, but also microbial based sources such as algae, bacteria, moulds and filamentous fungi etc. Re-use of spent oil from food industry is also considered a renewable source as well as oils obtained by conversion of wastes, such as municipal and slaughterhouse wastes.

(12) Here the term hydrotreatment includes at least hydrodeoxygenation (HDO) and is understood as a collective term for all catalytic processes, which removes oxygen from organic oxygen compounds in the form of water, sulphur from organic sulphur compounds in the form of dihydrogen sulphide (H.sub.2S), nitrogen from organic nitrogen compounds in the form of ammonia (NH.sub.3) (hydrodenitrogenation, HDN) and halogens, for example chlorine from organic chloride compounds in the form of hydrochloric acid (HCl) (hydrodechlorination, HDCl), for example, under the influence of sulphided NiMo or sulphided CoMo catalysts. Hydrotreatment is here understood to include also decarboxylation/decarbonylation, i.e., removal of oxygen in the form of CO.sub.x.

(13) Hydroisomerisation or isomerisation is here understood to mean any process in which branches on the hydrocarbon backbone are formed and isoparaffins are produced. For example, methyl and ethyl side-chains are formed in the isomerisation step.

(14) Disclosed is the use of bio oil, for example, glyceride oil, from at least one renewable source in a hydrotreatment process, in which process hydrocarbons are converted from the bio oil in a catalytic reaction and the iron content of the bio oil is less than 1 w-ppm, for example, less than 0.5 w-ppm, and, for example, less than 0.25 w-ppm, calculated as elemental iron. The hydrotreatment process is any catalytic process, such as a hydrodeoxygenation process performed using a trickle-bed reactor, in which, for example, glyceride oil material is treated with hydrogen to form hydrocarbons. Hydrodeoxygenation can be performed under a pressure from 10 to 150 bar, at a temperature of from 200 to 400° C. and using a hydrogenation catalyst containing metals from Group VIII and/or VIB of the Periodic System. For example, the hydrogenation catalysts are supported Pd, Pt, Ni, NiMo or CoMo catalyst, the support being alumina and/or silica. Exemplary catalysts are NiMo/Al203 and CoMo/Al203.

(15) In order to improve the properties, especially the cold flow properties, of the formed hydrocarbons, the hydrotreatment step can be followed by an isomerisation step. In the isomerisation step the hydrocarbons undergo an isomerisation reaction whereby isoparaffins are formed.

(16) A rapid increase in the pressure drop of the hydrotreatment reactor was noticed to occur in large scale production facilities. The reactor was opened and a substantial amount of dust-like particles was found inside the reactor. The dust-like particles were believed to be the cause of the plugging and increase in pressure drop over the catalyst bed. Analyses of dust-like particles revealed metals originating from feedstock (mainly Fe, Ca, Mg, Na) as well as phosphorus and carbon. Introducing less contaminated feedstock into the process has dramatically decreased the rate of pressure drop increase in the hydrotreating reactor. The plugging phenomenon was studied in more detail with a set of laboratory reactor experiments illustrated in the examples.

(17) Based on the experiments with palm oil having very low level of impurities, a catalyst cycle length based on catalyst deactivation with pure feedstock can be calculated. Furthermore, based on plant operating experience the rate of reactor plugging can be correlated with iron content. From this information, it can be concluded that bio-based feedstock (glyceride oil) to be used as feed material for hydrotreatment reaction can be purified to iron content of less than 1 to 0.2 w-ppm (depending on the dimensioning design WHSV of the hydrodeoxygenation reactor and expected life cycle of the catalyst), for example, in order not to shorten the catalyst cycle length due to pressure drop increase. For efficient and profitable plant operation, the Fe content of the feedstock of the hydrogenation reactor can be less than 0.5 w-ppm, for example, less than 0.25 w-ppm (w-ppm refers here to ppm by weight). This purification result can be obtained (depending on used feedstock) using pre-treatment methods, such as degumming and bleaching, or alternatively new pre-treatment technologies or a combination thereof. Thus, disclosed is a glyceride oil intermediate, which intermediate consists of glyceride oil from at least one renewable source and the iron content of said glyceride oil is less than 1 w-ppm calculated as elemental iron, for example, less than 0.5 w-ppm and, for example, less than 0.25 w-ppm.

EXAMPLES

(18) Undiluted glyceride oil was fed with high WHSV (8-10) through a bed consisting of hydrotreatment catalyst diluted in 1:2 ratio with quartz sand. Sand dilution was estimated to act as a filter, magnifying the plugging effect of the dust-like particles. This setup enabled reactor plugging to occur in days rather than months as in a reactor on an industrial scale plant. The reactor was considered to be plugged when a pressure drop of 3 bar was reached across the reactor, initial pressure being bar.

(19) First, a reference run (plant reference run) was conducted with degummed palm oil as the glyceride oil feed having rather high level of impurities (Experiment 1). Experiment 1 was repeated (Experiment 2). This test was repeated without any catalyst to demonstrate the effect of presence of catalyst in reactor plugging (Experiment 6). Experiments were then continued with bleached palm oil having very low levels of impurities (Experiment 3), filtered animal fat with high levels of P and Na but almost no other metals (Experiment 4), and finally bleached animal fat with moderate levels of P and Fe but almost no other metals (Experiment 5).

(20) A summary of the conducted experiments is shown below: Plant reference run with degummed palm oil (Experiment 1) Repetition of experiment 1 with degummed palm oil (Experiment 2) A run with bleached palm oil (Experiment 3) A run with filtered animal fat (Experiment 4) A run with bleached animal fat (Experiment 5) A run with degummed palm oil repeated without catalyst (Experiment 6)

(21) The composition of the dust-like particles was determined and the amount of the dust-like particles was measured after the experiment by separating the quartz sand and dust-like particles from the catalyst by screening and analysing the sand+dust mixture with wave length dispersive a X-ray fluorescence spectrometer (Bruker AXS S4 Explorer), with helium as measurement atmosphere.

(22) The results of the analyses in the experiments are shown in following Table 1.

(23) TABLE-US-00001 TABLE 1 Total increase in pressure drop, total cumulative feed through reactor; feed impurity levels, impurities found in catalyst, impurities found in sand + dust Experiment No. 1 2 3 4 5 6 Initial dP/bar 0.55 0.62 0.62 0.62 0.61 0.59 Final dP/bar 3.8 2.9 2.5 1.6 4.44 1.0 delta(dP)/bar 3.25 2.28 1.88 0.98 3.83 0.41 Cumulative 31.8 31.6 10.27 25.3 22.6 28.9 feed kg Plugging rate 102.1 72.1 18.3 38.8 169.7 14.2 mbar/kgfeed Feed impurity concentrations P/ppm 3.8 3.7 0.6 24 5.7 3.8 Ca/ppm 1.2 1.1 0.3 0.6 0.1 1.2 Fe/ppm 1.2 1.3 0.6 0.1 1.8 1.2 Na/ppm 1 0 0 6 0 1 Mg/ppm 0.2 0 0 0.3 0.2 0.2 Impurities found in sand + dust P/mg 425 309 154 154 309 301 Ca/mg 77 77 4 4 0 6 Fe/mg 116 116 77 54 174 18 Na/mg 77 39 0 54 0 6 Mg/mg 0 0 0 4 0 0 Impurities found in catalyst P/mg 60 50 20 206 30 Ca/mg 10 7 5 1 0 Fe/mg 30 22.5 85 14 70 Na/mg 10 12 5 13 0 Mg/mg 0 0 0 0 0
The pressure drop correlated with cumulative feed in each Experiment is presented in FIG. 1.

(24) The absolute amounts of individual impurities in the dust-like particles were then correlated with the absolute pressure drop increases in corresponding experiment. Results are shown as correlation plots with R2-values for P and Fe in FIG. 2 and for all measured impurities in Table 2 below.

(25) TABLE-US-00002 TABLE 2 Correlation between absolute increase in pressure drop and absolute masses of impurities found in dust Impurity R.sup.2 p 0.27 Ca 0.12 Fe 0.93 Na 0.01 Mg 0.18

(26) A relative plugging rate can be calculated for each experiment by dividing the increase in pressure drop with total cumulative feed introduced in the reactor throughout the experiment. Correlating this plugging rate with impurities in corresponding feedstocks gives the plots shown in FIG. 3 for P and Fe. This correlation for all measured impurities is shown in table 3. The experiment without catalyst is excluded from FIG. 3, due to different rate of dust formation with and without catalyst.

(27) TABLE-US-00003 TABLE 3 Correlation between rate of increase in pressure drop (in bar/ kg(feed) and concentrations of impurities in feed. Impurity R.sup.2 p 0.04 Ca 0.02 Fe 0.75 Na 0.14 Mg 0.10

(28) According to these results, iron is the only impurity in the dust correlating strongly with the increase in pressure drop over the catalyst bed.

(29) It will be appreciated by those skilled in the art that the present invention can be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The presently disclosed embodiments are therefore considered in all respects to be illustrative and not restricted. The scope of the invention is indicated by the appended claims rather than the foregoing description and all changes that come within the meaning and range and equivalence thereof are intended to be embraced therein.