WO2024195568A1 - Chlorine compound removing agent for removing chlorine compounds from liquid hydrocarbon - Google Patents

Abstract

Problem: The purpose of the present invention is to provide an organic chlorine compound removing agent capable of sufficiently removing chlorine compounds from a liquid hydrocarbon fluid. Solution: The present invention pertains to a chlorine compound removing agent for removing chlorine compounds from liquid hydrocarbon, the agent comprising: 1-40 wt% of zinc oxide; 5-40 wt% of a basic compound, where the basic compound is selected from the group consisting of alkali metal compounds, alkaline earth metal compounds, and a combination thereof; 10-85 wt% of zeolite; and 5-50 wt% of a binder. Here, wt% is based on the weight of the chlorine compound removing agent.

Description

Chlorine compound remover for removing chlorine compounds from liquid hydrocarbons

The present invention relates to a chlorine compound remover for removing chlorine compounds from liquid hydrocarbons.

In general, in the oil refining process, liquid hydrocarbons such as reformed gasoline contain inorganic chlorine compounds such as hydrogen chloride and organic chlorine compounds. These chlorine compounds corrode the equipment used in the oil refining process, so they need to be removed.

Reference 1 (JP 2001-072984) discloses an organic chlorine compound remover containing as main components (a) zinc oxide, (b) a binder, and (c) at least one basic compound selected from the group consisting of alkali metal compounds and alkaline earth metal compounds, and a method for removing inorganic and organic chlorine compounds from liquid hydrocarbon fluids using the same.

JP2001-072984

In recent years, in order to improve the efficiency of the petroleum refining process, there is a demand for a remover that can remove more chlorine compounds from liquid hydrocarbon fluids. The chlorine compounds contained in liquid hydrocarbon fluids include inorganic chlorine compounds such as hydrogen chloride, and organic chlorine compounds in which chlorine is added to carbon or hydrocarbons. In general, it is required to remove both inorganic chlorine compounds and organic chlorine compounds, or either one of them. Furthermore, conventional chlorine compound removers can generate chlorides, which are solid acids, on the surface of the remover that adsorbs inorganic chlorine compounds during the process of contacting the liquid hydrocarbon fluid. Due to the solid acidity of the surface of the remover, the hydrocarbons in the fluid react with hydrogen chloride to generate organic chlorine compounds, and there is also the problem that the concentration of organic chlorine compounds increases during the process of contacting the remover with the hydrocarbons.

The objective is to provide a chlorine compound remover that can sufficiently remove chlorine compounds from liquid hydrocarbon fluids.

One aspect of the present invention is a chlorine compound remover for removing chlorine compounds from liquid hydrocarbons, comprising 1-40 wt. % zinc oxide, 5-40 wt. % basic compound, where the basic compound is selected from the group consisting of alkali metal compounds, alkaline earth metal compounds, and combinations thereof, 10-85 wt. % zeolite, and 5-50 wt. % binder, where the wt. % is based on the weight of the chlorine compound remover.

Another aspect of the present invention is a method for removing chlorine compounds from liquid hydrocarbons, comprising the step of contacting the liquid hydrocarbons with the chlorine compound remover.

Another aspect of the present invention is a method for producing the chlorine compound remover, comprising the steps of mixing zinc oxide, a basic compound, a zeolite, and a binder to obtain a mixture, molding the mixture to obtain a molded body, and calcining the molded body.

Another aspect of the present invention is the use of said chlorine compounds to remove chlorine compounds from liquid hydrocarbons.

The present invention provides a chlorine compound remover that can sufficiently remove chlorine compounds from liquid hydrocarbon fluids.

A chlorine compound remover for removing chlorine compounds from liquid hydrocarbons comprises 1-40 wt. % zinc oxide, 5-40 wt. % basic compound, 10-85 wt. % zeolite, and 5-50 wt. % binder, where the wt. % is based on the weight of the chlorine compound remover.

"Fluid" refers to liquid hydrocarbon fluids unless otherwise specified.
Unless otherwise specified, "weight %" represents a weight percentage based on the weight of the chlorine compound removing agent.
Unless otherwise specified, the term "scavenger" refers to a chlorine compound scavenger.
The term "removal method" means a method for removing chlorine compounds from liquid hydrocarbons, unless otherwise specified.

The zinc oxide is 1 to 40% by weight based on the weight of the chlorine compound remover. In one embodiment, the zinc oxide is 3 to 39% by weight, in another embodiment, 5 to 38% by weight, in another embodiment, 6 to 37% by weight, in another embodiment, 7.5 to 37.5% by weight, in another embodiment, 8 to 37% by weight, in another embodiment, 8.5 to 36.5% by weight, in another embodiment, 9 to 36% by weight, in another embodiment, 9.5 to 35.5% by weight, in another embodiment, 10 to 33% by weight, in another embodiment, 10 to 22% by weight, in another embodiment, 10.5 to 32% by weight, in another embodiment, 11 to 31% by weight, in another embodiment, 1 1.5-30% by weight, in another embodiment 12-28% by weight, in another embodiment 15-26% by weight, in another embodiment 17-24% by weight, in another embodiment 19-21% by weight, in another embodiment 3-25% by weight, in another embodiment 5-24.5% by weight, in another embodiment 6-24% by weight, in another embodiment 7.5-23% by weight, in another embodiment 8-23.5% by weight, in another embodiment 8.5-23% by weight, in another embodiment 9-22.8% by weight, in another embodiment 9.5-22.5% by weight.

The specific surface area of the zinc oxide is in one embodiment from 20 to 100 m ² /g, and in another embodiment from 40 to 100 m ² /g.

The basic compound is selected from the group consisting of alkali metal compounds, alkaline earth metal compounds, and combinations thereof.

In another embodiment, the basic compound includes an alkali metal compound. In one embodiment, the alkali metal compound included in the basic compound includes an element selected from the group consisting of sodium, potassium, lithium, and combinations thereof. In another embodiment, the alkali metal compound included in the basic compound includes sodium.

In another embodiment, the basic compound includes an alkaline earth metal compound. In one embodiment, the alkaline earth metal compound included in the basic compound includes an element selected from the group consisting of magnesium, calcium, barium, strontium, and combinations thereof. In another embodiment, the alkaline earth metal compound included in the basic compound includes an element selected from the group consisting of magnesium, calcium, and combinations thereof. In another embodiment, the alkaline earth metal compound included in the basic compound includes calcium.

In another embodiment, the basic compound comprises an element selected from the group consisting of sodium, potassium, lithium, magnesium, calcium, barium, strontium, and combinations thereof. In another embodiment, the basic compound comprises an element selected from the group consisting of sodium, calcium, and combinations thereof.

In one embodiment, the basic compound comprises a compound selected from the group consisting of oxides, hydroxides, carbonates, bicarbonates, and combinations thereof. In another embodiment, the basic compound comprises a compound selected from the group consisting of oxides, hydroxides, carbonates, bicarbonates, and combinations thereof. In another embodiment, the basic compound comprises a compound selected from the group consisting of hydroxides, carbonates, bicarbonates, and combinations thereof. In another embodiment, the basic compound comprises a compound selected from the group consisting of hydroxides, carbonates, bicarbonates, and combinations thereof. In another embodiment, the basic compound comprises a compound selected from the group consisting of hydroxides, bicarbonates, and combinations thereof. In another embodiment, the basic compound comprises a hydroxide. In another embodiment, the basic compound is a hydroxide.

In another embodiment, the basic compound comprises a compound selected from the group consisting of an alkali metal oxide, an alkali metal hydroxide, an alkali metal carbonate, an alkali metal bicarbonate, an alkaline earth metal oxide, an alkaline earth metal hydroxide, an alkaline earth metal carbonate, an alkaline earth metal bicarbonate, and combinations thereof. In another embodiment, the basic compound comprises a compound selected from the group consisting of an alkali metal oxide, an alkali metal hydroxide, an alkali metal carbonate, an alkali metal bicarbonate, an alkaline earth metal oxide, an alkaline earth metal hydroxide, an alkaline earth metal carbonate, an alkaline earth metal bicarbonate, and combinations thereof. In another embodiment, the basic compound comprises a compound selected from the group consisting of an alkali metal carbonate, an alkali metal bicarbonate, an alkaline earth metal hydroxide, and combinations thereof. In another embodiment, the basic compound comprises a compound selected from the group consisting of an alkali metal carbonate, an alkali metal bicarbonate, an alkaline earth metal hydroxide, and combinations thereof. In another embodiment, the basic compound comprises a compound selected from the group consisting of an alkali metal carbonate, an alkali metal bicarbonate, an alkaline earth metal hydroxide, and combinations thereof. In another embodiment, the basic compound comprises a compound selected from the group consisting of alkali metal bicarbonates, alkaline earth metal hydroxides, and combinations thereof. In another embodiment, the basic compound comprises a compound selected from the group consisting of alkali metal bicarbonates, alkaline earth metal hydroxides, and combinations thereof.

In another embodiment, the basic compound comprises a compound selected from the group consisting of sodium bicarbonate, magnesium hydroxide, calcium hydroxide, and combinations thereof. In another embodiment, the basic compound comprises a compound selected from the group consisting of sodium bicarbonate, magnesium hydroxide, calcium hydroxide, and combinations thereof. In another embodiment, the basic compound comprises a compound selected from the group consisting of sodium bicarbonate, calcium hydroxide, and combinations thereof. In another embodiment, the basic compound comprises sodium bicarbonate. In another embodiment, the basic compound is sodium bicarbonate. In another embodiment, the basic compound comprises calcium hydroxide. In another embodiment, the basic compound is calcium hydroxide.

The basic compound is 5 to 40% by weight based on the weight of the chlorine compound remover. In one embodiment, the basic compound is 6 to 37% by weight, in another embodiment, 7 to 34% by weight, in another embodiment, 8 to 30% by weight, in another embodiment, 9 to 28% by weight, in another embodiment, 10 to 25% by weight, in another embodiment, 11 to 23% by weight, in another embodiment, 12 to 20% by weight, in another embodiment, 13 to 19% by weight, in another embodiment, 14 to 18% by weight, in another embodiment, 15 to 17% by weight, in another embodiment, 5 to 38% by weight, in another embodiment, 7 to 33% by weight, in another embodiment, 9 to 31.5% by weight, in another embodiment, 11 to 30% by weight, in another embodiment, 12.5 to 28% by weight, in another embodiment, 13.5 to 27% by weight, in another embodiment, 15 to 26% by weight.

Zeolites are hydrous aluminosilicates or hydrous silicates of clay minerals. In one embodiment, the zeolite is a hydrous aluminosilicate. In one embodiment, the zeolite contains a metal selected from the group consisting of alkali metals, alkaline earth metals, and combinations thereof.

In one embodiment, the zeolite contains an alkali metal. The alkali metal contained in the zeolite is calculated as the oxide and is based on the weight of the zeolite, in one embodiment 1-40 wt%, in another embodiment 1-36 wt%, in another embodiment 1-31 wt%, in another embodiment 1-26 wt%, in another embodiment 1-20 wt%, in another embodiment 2-30 wt%, in another embodiment 2-25 wt%, in another embodiment 2-20 wt%, in another embodiment 3-30 wt%, in another embodiment 3-25 wt%, in another embodiment 3-20 wt%, in another embodiment 4-30 wt%, in another embodiment 4-25 wt%, in another embodiment 4-20 wt%, in another embodiment 8-30 wt%, in another embodiment 8-25 wt%, in another embodiment 8-20 wt%, in another embodiment 14-30 wt%, in another embodiment 14-25 wt%, in another embodiment 14-20 wt%.

In one embodiment, the alkali metal in the zeolite is selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and combinations thereof. In another embodiment, the alkali metal in the zeolite is selected from the group consisting of Li, Na, K, and combinations thereof. In another embodiment, the alkali metal in the zeolite is selected from the group consisting of Na, Li, and combinations thereof. In another embodiment, the alkali metal in the zeolite is selected from the group consisting of K, Na, and combinations thereof. In another embodiment, the alkali metal in the zeolite includes K. In another embodiment, the alkali metal in the zeolite includes Na. In another embodiment, the alkali metal in the zeolite includes Na and K.

In another embodiment, the zeolite comprises an alkaline earth metal. The alkaline earth metal in the zeolite is present in an amount of 0.1 to 20 wt. %, in another embodiment 0.1 to 17 wt. %, in another embodiment 0.1 to 12 wt. %, in another embodiment 0.1 to 8 wt. %, in another embodiment 0.1 to 5 wt. %, in another embodiment 0.1 to 3 wt. %, in another embodiment 0.1 to 2.5 wt. %, in another embodiment 0.1 to 1 wt. %, in another embodiment 0.2 to 20 wt. %, based on the weight of the zeolite, calculated as the oxide. %, in another embodiment 0.2-12% by weight, in another embodiment 0.2-5% by weight, in another embodiment 0.2-3% by weight, in another embodiment 0.2-2.5% by weight, in another embodiment 0.2-1% by weight, in another embodiment 0.3-20% by weight, in another embodiment 0.3-12% by weight, in another embodiment 0.3-5% by weight, in another embodiment 0.3-3% by weight, in another embodiment 0.3-2.5% by weight, in another embodiment 0.3-1% by weight.

In one embodiment, the alkaline earth metals contained in the zeolite are selected from the group consisting of calcium (Ca), strontium (Sr), barium (Ba), radium (Ra), beryllium (Be), magnesium (Mg), and combinations thereof. In another embodiment, the alkaline earth metals contained in the zeolite are selected from the group consisting of Ca, Sr, Ba, Mg, and combinations thereof. In another embodiment, the alkaline earth metals contained in the zeolite are selected from the group consisting of Ca, Mg, and combinations thereof. In another embodiment, the alkaline earth metals contained in the zeolite include Ca. In another embodiment, the alkaline earth metals contained in the zeolite include Mg. In another embodiment, the alkaline earth metals contained in the zeolite include Ca and Mg.

In another embodiment, the zeolite comprises an alkali metal and an alkaline earth metal. The alkali metal and alkaline earth metal in the zeolite, calculated as oxide, are in one embodiment 1-40 wt%, in another embodiment 1-36 wt%, in another embodiment 1-31 wt%, in another embodiment 1-26 wt%, in another embodiment 1-20 wt%, in another embodiment 2-30 wt%, in another embodiment 2-25 wt%, in another embodiment 2-20 wt%, in another embodiment 3-30 wt%, in another embodiment 3-25 wt%, and in another embodiment 3-20 wt%, based on the weight of the zeolite.

In one embodiment, the zeolite comprises a metal selected from the group consisting of Li, Na, K, Rb, Cs, Ca, Sr, Ba, Ra, Be, Mg, and combinations thereof. In another embodiment, the zeolite comprises a metal selected from the group consisting of Li, Na, K, Cs, Ca, Sr, Ba, Mg, and combinations thereof. In another embodiment, the zeolite comprises a metal selected from the group consisting of Na, K, Ca, Mg, and combinations thereof. In another embodiment, the zeolite comprises Na, K, Ca, Mg. In another embodiment, the zeolite comprises Na.

In one embodiment, the zeolite is a hydrous aluminosilicate. The element ratio (Si/Al ratio) of silicon (Si) and aluminum (Al) contained in the hydrous aluminosilicate is, in one embodiment, 0.1 to 25.0, in another embodiment, 0.3 to 22.5, in another embodiment, 0.3 to 20.5, in another embodiment, 0.4 to 16.0, in another embodiment, 0.5 to 13.8, in another embodiment, 0.6 to 11.2, in another embodiment, 0.7 to 9.7, in another embodiment, 0.8 to 7.2, in another embodiment, 0.9 to 5.8, in another embodiment, 0.3 to 4.5, in another embodiment, 0.4 to 4.0, in another embodiment, 0.5 to 3.8, in another embodiment, 0.6 to 3.2 In another embodiment, it is 0.7 to 2.7, in another embodiment, it is 0.8 to 2.2, in another embodiment, it is 0.9 to 1.8, in another embodiment, it is 1.0 to 1.5, in another embodiment, it is 1.1 to 1.2, in another embodiment, it is 2.0 to 6.5, in another embodiment, it is 2.4 to 6.0, in another embodiment, it is 2.8 to 5.8, in another embodiment, it is 3.3 to 5.3, in another embodiment, it is 3.7 to 4.8, in another embodiment, it is 4.1 to 4.5, in another embodiment, it is 0.1 to 6.0, in another embodiment, it is 0.2 to 5.8, in another embodiment, it is 0.5 to 5.3, in another embodiment, it is 0.7 to 4.8, in another embodiment, it is 1.0 to 4.5.

Zeolites have a three-dimensional crystal structure with a tetrahedral structure of silica or alumina as the basic unit. Zeolites are classified according to the skeleton of their crystal structure. The skeleton of a zeolite's crystal structure can be identified by XRD measurement. Zeolites are given skeleton codes by the International Zeolite Society based on differences in their skeleton structures.

In one embodiment, the zeolite is selected from the group consisting of beta type (BEA), Y type (FAU), X type (FAU), L type (LTL), A type (LTA), MCM-22 (MWW), mordenite (MOR), ferrierite (FER), ZSM-5 (MFI), and combinations thereof. In another embodiment, the zeolite is selected from the group consisting of beta type, Y type, X type, L type, A type, mordenite, ferrierite, and combinations thereof. In another embodiment, the zeolite is selected from the group consisting of Y type, X type, L type, A type, mordenite, ferrierite, and combinations thereof. In another embodiment, the zeolite is selected from the group consisting of Y type, X type, L type, mordenite, and combinations thereof. In another embodiment, the zeolite is selected from the group consisting of X type, L type, mordenite, and combinations thereof.

In another embodiment, the zeolite is selected from the group consisting of X-type, mordenite, and combinations thereof. In another embodiment, the zeolite includes X-type. In another embodiment, the zeolite is X-type. In another embodiment, the zeolite includes mordenite. In another embodiment, the zeolite is mordenite. The X-type zeolite includes lithium type X-type zeolite (Li-X-type zeolite) in which the ion exchangeable cations in the zeolite are lithium ions, sodium type X-type zeolite (Na-X-type zeolite) in which the ion exchangeable cations are sodium ions, and potassium type X-type zeolite (K-X-type zeolite) in which the ion exchangeable cations are potassium ions. In another embodiment, the zeolite is an X-type zeolite selected from the group consisting of Li-X-type, Na-X-type, K-X-type, and combinations thereof. In another embodiment, the X-type zeolite includes Na-X-type (13X). In another embodiment, the X-type zeolite is Na-X-type (13X).

The zeolite is 10 to 85% by weight based on the weight of the chlorine compound remover. In one embodiment, the zeolite is 10 to 62% by weight, in another embodiment, 12 to 54% by weight, in another embodiment, 12 to 66% by weight, in another embodiment, 13 to 61% by weight, in another embodiment, 14 to 59% by weight, in another embodiment, 15 to 56% by weight, in another embodiment, 16 to 55% by weight, in another embodiment, 17 to 53% by weight, in another embodiment, 18 to 52% by weight, in another embodiment, 21 to 82% by weight, in another embodiment, 22 to 80% by weight, in another embodiment, 23 to 76% by weight, in another embodiment, 24 to 72% by weight based on the weight of the chlorine compound remover. , in another embodiment, 25-69% by weight, in another embodiment, 26-66% by weight, in another embodiment, 27-61% by weight, in another embodiment, 28-59% by weight, in another embodiment, 29-56% by weight, in another embodiment, 30-54% by weight, in another embodiment, 32-66% by weight, in another embodiment, 33-61% by weight, in another embodiment, 34-59% by weight, in another embodiment, 35-56% by weight, in another embodiment, 36-55% by weight, in another embodiment, 37-53% by weight, in another embodiment, 38-52% by weight, in another embodiment, 39-51% by weight.

In one embodiment, the binder comprises a clay selected from the group consisting of kaolin, gairome clay, kibushi clay, bentonite, sepiolite, attapulgite (palygorskite), talc, and combinations thereof. In another embodiment, the binder is a clay selected from the group consisting of kaolin, gairome clay, kibushi clay, bentonite, sepiolite, attapulgite, talc, and combinations thereof. In another embodiment, the binder comprises a clay selected from the group consisting of sepiolite, attapulgite, talc, and combinations thereof. In another embodiment, the binder is a clay selected from the group consisting of sepiolite, attapulgite, talc, and combinations thereof. In another embodiment, the binder comprises a clay selected from the group consisting of sepiolite, attapulgite, and combinations thereof. In another embodiment, the binder is a clay selected from the group consisting of sepiolite, attapulgite, and combinations thereof. In another embodiment, the binder comprises an attapulgite. In another embodiment, the binder is an attapulgite.

In another embodiment, the binder includes, in addition to clay, silica sol, water glass, alumina sol, aluminum hydroxide, boehmite-type hydrous alumina, etc.

The binder is 5 to 50% by weight based on the weight of the chlorine compound remover. In one embodiment, the binder is 6 to 49% by weight, in another embodiment, 7 to 48% by weight, in another embodiment, 8 to 45% by weight, in another embodiment, 9 to 43% by weight, in another embodiment, 10 to 41% by weight, in another embodiment, 11 to 39% by weight, in another embodiment, 12 to 37% by weight, in another embodiment, 13 to 35% by weight, in another embodiment, 14 to 34% by weight, in another embodiment, 15 to 33% by weight, in another embodiment, 16 to 3 2% by weight, in another embodiment 17-31% by weight, in another embodiment 18-30% by weight, in another embodiment 19-29% by weight, in another embodiment 20-28% by weight, in another embodiment 21-27% by weight, in another embodiment 22-26% by weight, in another embodiment 23-25% by weight, in another embodiment 19-35% by weight, in another embodiment 20.5-33% by weight, in another embodiment 22-31% by weight, in another embodiment 23-29% by weight.

The shape of the chlorine compound remover is not limited. The remover can be in any shape as long as it has sufficient removal ability and strength as a chlorine compound remover. In one embodiment, the shape of the remover is selected from a cylindrical shape, a spherical shape, a spiral shape, a tablet, a granule, a crushed grain, a powder, and combinations thereof. In another embodiment, the shape of the remover is a cylindrical shape. The inside of the cylindrical shape may be filled, hollow, honeycomb, or lattice-shaped.

In one embodiment, the cross section of the cylindrical chlorine compound remover is selected from the group consisting of a circle, an ellipse, a polygon, a rectangle, a polylobe, and a combination thereof. In another embodiment, the cross section of the cylindrical remover is selected from the group consisting of a circle, an ellipse, a polylobe, and a combination thereof. In another embodiment, the cross section of the cylindrical remover is poly-lobe. In one embodiment, the poly-lobe type is tri-lobe. By providing three grooves on the side of the cylinder, for example the side of a cylinder, the cross section becomes a tri-lobe shape including three lobes. In another embodiment, the shape of the remover is a cylinder with a circular cross section, i.e. a cylindrical shape. In another embodiment, the shape of the remover is a cylinder with a tri-lobe cross section.

The average diameter of the cross section of the chlorine compound remover is, in one embodiment, 0.1 to 30 mm, in another embodiment, 0.3 to 28 mm, in another embodiment, 0.4 to 24 mm, in another embodiment, 0.5 to 22 mm, in another embodiment, 0.7 to 20 mm, in another embodiment, 0.9 to 18 mm, in another embodiment, 1.0 to 15 mm, in another embodiment, 1.2 to 10 mm, in another embodiment, 1.3 to 8 mm, in another embodiment, 1.4 to 5 mm, in another embodiment, 1.5 to 4 mm, in another embodiment, 1.6 to 2 mm. The cross-sectional diameter of the chlorine compound remover means the diameter of the circle in a circular cross section, and the diameter of the circumscribing circle in a cross section other than a circular cross section.

The average length of the chlorine compound remover is, in one embodiment, 1 to 100 mm, in another embodiment, 1.3 to 89 mm, in another embodiment, 1.4 to 72 mm, in another embodiment, 1.5 to 63 mm, in another embodiment, 1.7 to 51 mm, in another embodiment, 1.9 to 44 mm, in another embodiment, 2.0 to 32 mm, in another embodiment, 2.2 to 20 mm, in another embodiment, 2.3 to 11 mm, in another embodiment, 2.4 to 7 mm, in another embodiment, 2.6 to 5 mm, and in another embodiment, 2.8 to 4 mm. The average diameter and average length of the cross section of the chlorine compound remover are the average measurements of 100 randomly selected removers.

The specific surface area (SA) of the chlorine compound removing agent is, in one embodiment, 30 to 500 ^{m 2} /g, in another embodiment, 30 to 490 m ² /g, in another embodiment, 30 to 480 m ² /g, in another embodiment, 30 to 450 m ² /g, in another embodiment, 30 to 430 m ² /g, in another embodiment, 30 to 420 m ² /g, in another embodiment, 32 to 415 m ² /g, in another embodiment, 34 to 410 m ² /g, in another embodiment, 35 to 400 m ² /g, in another embodiment, 35 to 390 m ² /g, in another embodiment, 35 to 380 m ² /g, in another embodiment, 35 to 150 m ² /g, and in another embodiment, 35 to 142 m ² /g, in another embodiment 35-132 m ² /g, in another embodiment 35-125 m ² /g, in another embodiment 35-120 m ² /g, in another embodiment 200-450 ^{m 2} /g, in another embodiment 210-440 m ² /g, in another embodiment 220-420 m ² /g, in another embodiment 230-400 m ² /g, in another embodiment 240-380 m ² /g, and in another embodiment 245-370 m ² /g.

The remover is a chlorine compound remover for removing chlorine compounds from liquid hydrocarbons. In one embodiment, the chlorine compound is selected from the group consisting of organic chlorine compounds, inorganic chlorine compounds, and combinations thereof. In another embodiment, the remover is a remover for removing either organic chlorine compounds or inorganic chlorine compounds from liquid hydrocarbons.

In one embodiment, the chlorine compound comprises an inorganic chlorine compound. In one embodiment, the remover is a chlorine compound remover for removing inorganic chlorine compounds from liquid hydrocarbons.

In one embodiment, the chlorine compound includes an organic chlorine compound. In one embodiment, the remover is a chlorine compound remover for removing organic chlorine compounds from liquid hydrocarbons.

In another embodiment, the chlorine compounds include both inorganic chlorine compounds and organic chlorine compounds. In one embodiment, the remover is a chlorine compound remover for removing both inorganic chlorine compounds and organic chlorine compounds from liquid hydrocarbons. In another embodiment, the remover is a chlorine compound remover for simultaneously removing both inorganic chlorine compounds and organic chlorine compounds from liquid hydrocarbons.

The method for producing the chlorine compound remover includes the steps of mixing zinc oxide, a basic compound, a zeolite, and a binder to obtain a mixture, shaping the mixture to obtain a molded body, and calcining the molded body.

In one embodiment, in the process of mixing zinc oxide, a basic compound, zeolite and a binder, the raw materials are thoroughly dry mixed in a mixer, kneader or muller, and then water is added to obtain a viscosity suitable for molding.

In one embodiment, the resulting mixture is shaped by extrusion or molding. In another embodiment, the extrusion is performed in an extruder or pelletizer. The shape of the shaped body is the same as that of the chlorine compound remover.

The calcination temperature is, in one embodiment, 200 to 500° C., in another embodiment, 250 to 400° C., and in another embodiment, 280 to 350° C. The calcination time is, in one embodiment, 10 minutes to 5 hours, in another embodiment, 30 minutes to 3.5 hours, and in another embodiment, 50 minutes to 2 hours.

In one embodiment, the method for producing a chlorine compound remover includes a step of drying the molded body before the calcination step. The drying temperature is 50 to 250°C in one embodiment, 70 to 200°C in another embodiment, 90 to 160°C in another embodiment, and 100 to 140°C in another embodiment. The drying time is 1 to 10 hours in one embodiment, 2.5 to 8 hours in another embodiment, and 4 to 6 hours in another embodiment.

In one embodiment, the shaped body is calcined to obtain a chlorine compound remover. In another embodiment, the calcined shaped body is crushed to a desired size. In another embodiment, the crushed shaped body can be sieved to obtain a chlorine compound remover in a granular form having a predetermined particle size.

The method for removing chlorine compounds from liquid hydrocarbons includes the step of contacting the liquid hydrocarbons with the chlorine compound remover.

In one embodiment, the liquid hydrocarbon comprises a liquid obtained by petroleum refining. The liquid hydrocarbon can be any of a variety of hydrocarbon fractions, regardless of boiling range. In another embodiment, the liquid hydrocarbon comprises a liquid selected from the group consisting of liquid natural gas, liquefied petroleum gas (LPG), gasoline, kerosene, naphtha, reformate, diesel fuel, and combinations thereof. In another embodiment, the liquid hydrocarbon comprises a liquid selected from the group consisting of naphtha, reformate, and combinations thereof. In another embodiment, the liquid hydrocarbon comprises a reformate. In another embodiment, the liquid hydrocarbon is a reformate.

In one embodiment, the liquid hydrocarbon is contacted with the chlorine compound removing agent at a temperature between 10 and 400°C. In another embodiment, the temperature at which the liquid hydrocarbon is contacted with the chlorine compound removing agent is between 10 and 350°C, between 10 and 300°C, between 10 and 250°C, between 10 and 200°C, between 10 and 150°C, between 10 and 100°C, between 10 and 80°C, and between 10 and 50°C.

The pressure at which the liquid hydrocarbon is contacted with the chlorine compound removal agent is 0.1 to 15 MPa in one embodiment, and 0.1 to 5 MPa in another embodiment.

The space time of the liquid hydrocarbon feed is, in one embodiment, 1 minute to 10 hours, in another embodiment, 1 minute to 8 hours, in another embodiment, 1 minute to 6 hours, in another embodiment, 1 minute to 3 hours, in another embodiment, 1 minute to 2 hours, in another embodiment, 1 minute to 100 minutes, in another embodiment, 1 minute to 90 minutes, and in another embodiment, 1 minute to 75 minutes.

The space time is expressed as space time (min) k=V/X, where Vm ³ is the volume of the removing agent and Xm ³ /min is the supply amount of the liquid hydrocarbon to be contacted with the removing agent.

In one embodiment, the chlorine compound removing agent can be loaded into a reactor, and liquid hydrocarbons can be contacted with the chlorine compound removing agent in the reactor. In one embodiment, the reactor includes a hydrocarbon inlet and an outlet for liquid hydrocarbons. In one embodiment, the reactor includes a fixed bed, a fluidized bed, a moving bed, or a combination thereof. In another embodiment, the reactor includes a fixed bed loaded with the removing agent. In another embodiment, the method includes a step of feeding liquid hydrocarbon feed through the inlet of the reactor and contacting it with the removing agent loaded in the reactor. The method allows liquid hydrocarbons from which chlorine compounds have been removed to be obtained from the outlet of the reactor.

As shown in the examples, the above remover is excellent at removing inorganic chlorine compounds, and can therefore also be used as an inorganic chlorine compound remover. In one embodiment, the removal method is a method for removing inorganic chlorine compounds from liquid hydrocarbons. In one embodiment, the liquid hydrocarbon contains inorganic chlorine compounds and is substantially free of organic chlorine compounds. "Substantially free of organic chlorine compounds" means that the liquid hydrocarbon contains zero organic chlorine compounds or, if any, 0.1 ppm or less.

As shown in the examples, the above remover is also excellent at removing organic chlorine compounds, and can therefore also be used as an organic chlorine compound remover. In one embodiment, the removal method is a method for removing organic chlorine compounds from liquid hydrocarbons. In one embodiment, the liquid hydrocarbon contains organic chlorine compounds and is substantially free of inorganic chlorine compounds. "Substantially free of inorganic chlorine compounds" means that the liquid hydrocarbon contains zero inorganic chlorine compounds or, if any, 0.1 ppm or less.

As shown in the examples, the remover is excellent at removing both inorganic chlorine compounds and organic chlorine compounds, and therefore can be used as a remover for both inorganic chlorine compounds and organic chlorine compounds. In one embodiment, the removal method is a method for removing both inorganic chlorine compounds and organic chlorine compounds from liquid hydrocarbons. In the method for removing both inorganic chlorine compounds and organic chlorine compounds, both inorganic chlorine compounds and organic chlorine compounds may be removed from liquid hydrocarbons simultaneously, or inorganic chlorine compounds and organic chlorine compounds may be removed in separate steps.

When inorganic chlorine compounds and organic chlorine compounds are removed in separate steps, the step of removing inorganic chlorine compounds and the step of removing organic chlorine compounds may be performed independently at different times and places, or may be performed consecutively in time and place. The above-mentioned chlorine compound remover can be used in either the step of removing inorganic chlorine compounds or the step of removing organic chlorine compounds.

In one embodiment, the method for removing chlorine compounds from liquid hydrocarbons includes (b) contacting the liquid hydrocarbon with the chlorine compound removing agent of the present invention to remove inorganic chlorine compounds from the liquid hydrocarbon, and (a) contacting the liquid hydrocarbon with another organic chlorine compound removing agent to remove organic chlorine compounds from the liquid hydrocarbon. In another embodiment, the method for removing chlorine compounds from liquid hydrocarbons includes (b) contacting the liquid hydrocarbon with the chlorine compound removing agent of the present invention to remove inorganic chlorine compounds from the liquid hydrocarbon, and then (a) contacting the liquid hydrocarbon with a reduced inorganic chlorine compound content with another organic chlorine compound removing agent to remove organic chlorine compounds from the liquid hydrocarbon. The "another organic chlorine compound removing agent" is a removing agent that removes organic chlorine compounds other than the chlorine compound removing agent of the present invention. For example, ActiSorb (registered trademark) Cl6 from Clariant.

In one embodiment, the method for removing chlorine compounds from liquid hydrocarbons includes (b) contacting the liquid hydrocarbon with another inorganic chlorine compound removing agent to remove inorganic chlorine compounds from the liquid hydrocarbon, and (a) contacting the liquid hydrocarbon with the chlorine compound removing agent of the present invention to remove organic chlorine compounds from the liquid hydrocarbon. In another embodiment, the method for removing chlorine compounds from liquid hydrocarbons includes (b) contacting the liquid hydrocarbon with another inorganic chlorine compound removing agent to remove inorganic chlorine compounds from the liquid hydrocarbon, and then (a) contacting the liquid hydrocarbon with a reduced inorganic chlorine compound content with the chlorine compound removing agent of the present invention to remove organic chlorine compounds from the liquid hydrocarbon. The "another inorganic chlorine compound removing agent" is a removing agent for removing inorganic chlorine compounds other than the chlorine compound removing agent of the present invention. For example, ActiSorb (registered trademark) C125 from Clariant.

The present invention will be specifically explained using examples and comparative examples. The present invention is not limited in any way by these examples.

Example 1, Comparative Examples 1 to 3
Preparation of chlorine compound remover Zinc oxide, attapulgite, calcium hydroxide and zeolite shown below were added in the amounts shown in Table 1, and dry mixed in a kneader for 10 minutes.
Zinc oxide: Activated zinc oxide AZO, Seido Chemical Industry Co., Ltd.
Attapulgite: Min-U-Gel® 200, Active Minerals International LLC
Calcium hydroxide: slaked lime, Ube Material Industries, Ltd.
Zeolite (13X): NAX zeolite (Na-containing hydrous aluminosilicate, Si/Al ratio: 1.16), Qingdao Wish Chemicals Co. Ltd.
Zeolite-mordenite (MOR): Nitto Zeolite #70 (Si/Al ratio: 4.24), Nitto Funka Kogyo Co., Ltd.

Then, the mixture was kneaded for another 10 minutes while gradually adding water to the kneader until the viscosity became suitable for extrusion molding. The resulting kneaded product was extruded. The extruded pellets had a trilobe-shaped columnar cross section. The pellets were dried at 120°C for 5 hours and then calcined at 300°C for 1 hour to prepare a chlorine compound remover. The size of the chlorine compound remover was a trilobe-shaped cross section with an average diameter of about 1.6 mm and an average length of about 3 mm.

Measurement method for specific surface area (SA) The specific surface area of the obtained remover was measured using a specific surface area measuring device (Macsorb (registered trademark) HM model-1201, MOUNTECH Co. Ltd.) based on the adsorption of nitrogen gas at liquid nitrogen temperature by the BET (single point) method in accordance with JIS Z8830:2013.

200 ml of reformate and 10 g of the above remover were placed in a HCl removal amount container. The RCl and HCl in the reformate were both 0.5 ppm or less, and were hardly contained. _N2 gas containing HCl was supplied to the reformate in the container through a tube while stirring, and HCl was saturated. The container containing the reformate saturated with HCl and the remover was left to stand for 3 hours. After that, the remover in the reformate was taken out and dried at 120 ° C., and the amount of HCl removed by each remover (HCl pick-up) was measured by Volhard titration method.

Reformate RCl
It is believed that RCl is generated in the reformate after the removal of the remover by reaction of the supplied HCl with the hydrocarbon in the reformate. The amount of RCl generated was measured by the following procedure. First, the reformate after the removal of the remover and pure water were mixed in a separatory funnel to extract HCl into the pure water. Then, the reformate containing RCl and the aqueous phase containing HCl were separated. The amount of RCl in the reformate was then measured by wavelength dispersive XRF (X-ray fluorescence analyzer, Supermini200, Rigaku Corporation).

Amount of RCl Removed Next, a new reformate was prepared, and the reformate was brought into contact with the remover, and the amount of RCl adsorbed by the remover from the reformate was measured by the following procedure.

1. First, a reformate containing about 100 ppm of RCl dissolved therein was prepared.
2.40 ml of the reformate and 2 g of each remover were placed in an Erlenmeyer flask.
3. The Erlenmeyer flask was shaken in a shaker at room temperature (about 25° C.) for 1 hour.
4. The remover in the Erlenmeyer flask was left behind, and the reformate was taken out. The amount of RCl in the removed reformate was measured using a wavelength dispersive small fluorescent X-ray analyzer (Supermini200, Rigaku Corporation). The amount of RCl adsorbed by each remover in this operation was determined by subtracting the amount of RCl obtained by each measurement from the amount of RCl in the reformate without the remover.
5. After that, without removing the remover from the Erlenmeyer flask, 40 ml of reformate containing 100 ppm was poured in and shaken for 1 hour in the same manner as above, and the amount of RCl adsorbed by each remover was measured in the same manner as above. Furthermore, the same procedure was repeated, and the total amount of RCl adsorbed by each remover after the above three repeated procedures was taken as the RCl pick-up for that remover.

The results are shown in Table 1. HCl pick-up, the amount of RCl in the reformate, and RCl pick-up were expressed as relative values with the measured value in Comparative Example 1 taken as 100.

HCl pick-up was lower in Comparative Examples 2 and 3 than in Comparative Example 1, but was higher in Example 1 than in Comparative Example 1. The amount of RCl in the reformate increased by about 5 times and about 8 times in Comparative Examples 2 and 3, respectively. This is thought to be because RCl was generated by the reaction of the supplied HCl with the hydrocarbons in the reformate. In contrast, in Example 1, the amount of RCl in the reformate decreased to about half of that in Comparative Example 1. RCl pick-up was about 2 to 3 times higher in Comparative Examples 2, 3, and Example 1 than in Comparative Example 1.

The above embodiments can be combined in any manner that is not technically or logically inconsistent. For example, the following embodiments can be mentioned:

Embodiment 1: A chlorine compound remover for removing chlorine compounds from liquid hydrocarbons, comprising 1-40 wt. % zinc oxide, 5-40 wt. % basic compound, where the basic compound is selected from the group consisting of alkali metal compounds, alkaline earth metal compounds, and combinations thereof, 10-85 wt. % zeolite, and 5-50 wt. % binder, where the wt. % is based on the weight of the chlorine compound remover.

Embodiment 2: The chlorine compound remover according to embodiment 1, wherein the basic compound includes a compound selected from the group consisting of oxides, hydroxides, carbonates, bicarbonates, and combinations thereof.

Embodiment 3: A chlorine compound remover according to embodiment 1 or embodiment 2, wherein the basic compound includes an element selected from the group consisting of sodium, potassium, lithium, magnesium, calcium, barium, strontium, and combinations thereof.

Embodiment 4: The chlorine compound remover according to embodiments 1 to 3, wherein the zeolite is selected from the group consisting of beta type (BEA), Y type (FAU), X type (FAU), L type (LTL), A type (LTA), MCM-22 (MWW), mordenite (MOR), ferrierite (FER), ZSM-5 (MFI), and combinations thereof.

Embodiment 5: The chlorine compound remover according to embodiments 1 to 4, wherein the zeolite is a hydrous aluminosilicate having a Si/Al ratio of 0.1 to 25.0.

Embodiment 6: The chlorine compound remover according to embodiments 1 to 5, wherein the binder comprises a clay selected from the group consisting of kaolin, gairome clay, kibushi clay, bentonite, sepiolite, attapulgite (palygorskite), talc, and combinations thereof.

Embodiment 7: The chlorine compound removing agent according to any one of embodiments 1 to 6, wherein the specific surface area (SA) of the chlorine compound removing agent is 30 to 500 m ² /g.

Embodiment 8: The chlorine compound remover according to embodiments 1 to 7, wherein the chlorine compound is selected from the group consisting of organic chlorine compounds, inorganic chlorine compounds, and combinations thereof.

Embodiment 9: A chlorine compound remover according to embodiments 1 to 8, wherein the chlorine compound includes both inorganic chlorine compounds and organic chlorine compounds.

Embodiment 10: A method for removing chlorine compounds from liquid hydrocarbons, comprising contacting the liquid hydrocarbons with the chlorine compound remover described in embodiment 1.

Embodiment 11: The method of embodiment 10, wherein the liquid hydrocarbon is contacted with the chlorine compound removing agent at 10 to 400°C.

Embodiment 12: The method of embodiment 10 or 11, wherein the chlorine compound is selected from the group consisting of organic chlorine compounds, inorganic chlorine compounds, and combinations thereof.

Embodiment 13: The method of embodiments 10 to 12, wherein the chlorine compounds include both inorganic and organic chlorine compounds.

Embodiment 14: A step of mixing zinc oxide, a basic compound, a zeolite and a binder to obtain a mixture.
shaping the mixture to obtain a shaped body, and calcining the shaped body;
The method for producing the chlorine compound removing agent of embodiment 1, comprising:

Embodiment 15: Use of the chlorine compound remover of embodiment 1 to remove chlorine compounds from liquid hydrocarbons.

Embodiment 16: Use of the chlorine compound remover of embodiment 1 to remove inorganic chlorine compounds from liquid hydrocarbons.

Embodiment 17: Use of the chlorine compound remover of embodiment 1 to remove organic chlorine compounds from liquid hydrocarbons.

Embodiment 18: Use of the chlorine compound remover of embodiment 1 to remove both inorganic and organic chlorine compounds from liquid hydrocarbons.

Embodiment 19: Use of the chlorine compound remover of embodiment 1 to simultaneously remove both inorganic and organic chlorine compounds from liquid hydrocarbons.

Embodiment 20: A chlorine compound remover for removing chlorine compounds from liquid hydrocarbons, comprising 1-40 wt. % zinc oxide; 5-40 wt. % basic compound, wherein the basic compound is selected from the group consisting of alkali metal compounds, alkaline earth metal compounds, and combinations thereof; 10-85 wt. % zeolite, wherein the zeolite is selected from the group consisting of beta type (BEA), Y type (FAU), X type (FAU), L type (LTL), A type (LTA), MCM-22 (MWW), mordenite (MOR), ferrierite (FER), ZSM-5 (MFI), and combinations thereof; and 5-50 wt. % binder, wherein the binder comprises a clay selected from the group consisting of kaolin, gairome clay, kibushi clay, bentonite, sepiolite, attapulgite (palygorskite), talc, and combinations thereof, wherein the weight % is based on the weight of the chlorine compound remover.

Embodiment 21: 1 to 40% by weight of zinc oxide; 5 to 40% by weight of a basic compound, wherein the basic compound comprises an element selected from the group consisting of sodium, potassium, lithium, magnesium, calcium, barium, strontium, and combinations thereof; 10 to 85% by weight of a zeolite, wherein the zeolite is selected from the group consisting of beta type (BEA), Y type (FAU), X type (FAU), L type (LTL), A type (LTA), MCM-22 (MWW), mordenite (MOR), fulvelite (FUL), fluorite ... A chlorine compound remover for removing chlorine compounds from liquid hydrocarbons, comprising: a binder selected from the group consisting of ferrierite (FER), ZSM-5 (MFI), and combinations thereof; and 5-50 wt. % of a binder, wherein the binder comprises a clay selected from the group consisting of kaolin, gairome clay, kibushi clay, bentonite, sepiolite, attapulgite (palygorskite), talc, and combinations thereof, wherein the wt. % is based on the weight of the chlorine compound remover.

Embodiment 22: 1 to 40% by weight of zinc oxide; 5 to 40% by weight of a basic compound, wherein the basic compound is a compound selected from the group consisting of oxides, hydroxides, carbonates, bicarbonates, and combinations thereof, and the basic compound includes an element selected from the group consisting of sodium, potassium, lithium, magnesium, calcium, barium, strontium, and combinations thereof; 10 to 85% by weight of a zeolite, wherein the zeolite is a beta type (BEA), Y type (FAU), X type (FAU), L type (LTL), A type (LTL), (LTA), MCM-22 (MWW), mordenite (MOR), ferrierite (FER), ZSM-5 (MFI), and combinations thereof; and 5 to 50 weight percent of a binder, where the binder comprises a clay selected from the group consisting of kaolin, gairome clay, kibushi clay, bentonite, sepiolite, attapulgite (palygorskite), talc, and combinations thereof, where the weight percent is based on the weight of the chlorine compound remover, a chlorine compound remover for removing chlorine compounds from liquid hydrocarbons.

23. A chlorine compound removing agent for removing chlorine compounds from liquid hydrocarbons comprising: 1-40 wt. % zinc oxide; 5-40 wt. % of a basic compound, wherein the basic compound is selected from the group consisting of an alkali metal compound, an alkaline earth metal compound, and combinations thereof; 10-85 wt. % of a zeolite, wherein the zeolite comprises an alkali metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and combinations thereof; and 5-50 wt. % of a binder, wherein the binder comprises a clay selected from the group consisting of kaolin, gairome clay, kibushi clay, bentonite, sepiolite, attapulgite (palygorskite), talc, and combinations thereof, wherein the weight percent is based on the weight of the chlorine compound removing agent.

Claims (14)

1 to 40% by weight of zinc oxide,
5 to 40 wt. % of a basic compound, wherein the basic compound is selected from the group consisting of alkali metal compounds, alkaline earth metal compounds, and combinations thereof;
10-85 wt. % zeolite, and 5-50 wt. % binder;
Here, weight percent is based on the weight of the chlorine compound removing agent.
A chlorine compound remover for removing chlorine compounds from liquid hydrocarbons. The chlorine compound remover according to claim 1, wherein the basic compound includes a compound selected from the group consisting of oxides, hydroxides, carbonates, bicarbonates, and combinations thereof. The chlorine compound remover according to claim 1, wherein the basic compound includes an element selected from the group consisting of sodium, potassium, lithium, magnesium, calcium, barium, strontium, and combinations thereof. The chlorine compound remover according to claim 1, wherein the zeolite is selected from the group consisting of beta type (BEA), Y type (FAU), X type (FAU), L type (LTL), A type (LTA), MCM-22 (MWW), mordenite (MOR), ferrierite (FER), ZSM-5 (MFI), and combinations thereof. The chlorine compound remover according to claim 1, wherein the zeolite is a hydrous aluminosilicate having a Si/Al ratio of 0.1 to 25.0. The chlorine compound remover according to claim 1, wherein the binder comprises a clay selected from the group consisting of kaolin, gairome clay, kibushi clay, bentonite, sepiolite, attapulgite (palygorskite), talc, and combinations thereof. The chlorine compound removing agent according to claim 1, wherein the specific surface area (SA) of the chlorine compound removing agent is 30 to 500 m ² /g. The chlorine compound remover according to claim 1, wherein the chlorine compound is selected from the group consisting of organic chlorine compounds, inorganic chlorine compounds, and combinations thereof. The chlorine compound remover according to claim 1, wherein the chlorine compounds include both inorganic chlorine compounds and organic chlorine compounds. A method for removing chlorine compounds from liquid hydrocarbons, comprising the step of contacting the liquid hydrocarbons with the chlorine compound remover of claim 1. The method according to claim 10, wherein the liquid hydrocarbon is contacted with the chlorine compound removing agent at 10 to 400°C. The method of claim 10, wherein the chlorine compound is selected from the group consisting of organic chlorine compounds, inorganic chlorine compounds, and combinations thereof. The method of claim 10, wherein the chlorine compounds include both inorganic and organic chlorine compounds. mixing zinc oxide, a basic compound, a zeolite and a binder to obtain a mixture;
shaping the mixture to obtain a shaped body, and calcining the shaped body;
A method for producing the chlorine compound remover of claim 1, comprising: