Table 3. An Overview of Patent Literature Describing Oxygenate-Mediated Processes for the Formation of Hydrocarbons from CO_x (x = 1, 2) and H₂^a.

								Hydrocarbon selectivity (%C)
Year	Company	Process (Feed)	Methanol synthesis catalyst	MTH cat.	T (°C)	P (bar)	X (% COx)	CH4	C2–4=	C2–40	C5+	ref.
1981	Metallgesellschaft	2-stage	Cu/Zn/V	H-ZSM-5	T1: 250	P1: 58	40	n.r.	n.r.	n.r.	n.r.	(47)
		COx, H2			T2: 375	P2: 58
2001	UOP/Norsk Hydro	3-stage	Cu/Zn/Cr	H-SAPO-34	T1: 150–450	P1: 1–103	n.r.	<1	96	1	2	(48)
		CH4		H-SAPO-17	T2: 200–700	P2: 1–5
2001	KAIST	H2/CO2 = 3	Cu/Zn/Zr	H-SAPO-5	350	28	32	4	89 (43% C4)		7	(49)
2001	KAIST	H2/CO2 = 3	Cu/Zn/Zr	Cu-SAPO-5	350	28	28	4	85 (49% C4)		12	(49)
2001	KAIST	H2/CO2 = 3	Cu/Zn/Zr	H-SAPO-34	400	28	35	4	96 (52% C3)		1	(49)
2001	KAIST	H2/CO2 = 3	Cu/Zn/Zr	Cu-SAPO-34	400	28	40	2	97 (55% C3)		1	(49)
2007	Japan Gas Synthesize	H2/CO = 2	Pd/Ca/Si	β-zeolite	375	41	74	7	0	84	9	(50)
2007	Japan Gas Synthesize	H2/CO = 2	Pd/Ca/Si	β-zeolite	375	51	87	8	0	87	5	(50)
2007	Japan Gas Synthesize	H2/CO = 2	Pd/Ca/Si	Y-zeolite	375	51	88	10	0	84	6	(50)
2011	Chevron	H2/CO = 2	Zn/Cr	H-ZSM-5	350	41	30	2	3	26	69	(51)
2011	Chevron	H2/CO = 2	Zn/Cr	Ga-ZSM-5	350	41	30	1	5	17	77	(51)
2013	Chevron	H2/CO/CO2 = 67/25/8	Zn/Cr	H-ZSM-5	380	81	23	1	1	26	72	(52)
2014	Sinopec	H2/CO/CO2 = 50/42/8	Cu/Al/K/C/Mn/Si	H-SAPO-34	290	10	91	n.r.	37	n.r.	n.r.	(53)
2016	Pioneer Energy	H2/CO = 2	Cu/Zn	Zn-ZSM-5	225–300	20	87	4	n.r.	84	9	(54)
2016	Pioneer Energy	H2/CO = 2	Cu/Zn/Al	Zn-ZSM-5	200–420	20	67	13	n.r.	84	3	(54)
2016	Pioneer Energy	2-stage	Cu/Zn/Al	Zn-ZSM-5	T1: 250	P1: 20	61	8	0	54	39	(54)
		H2/CO = 2			T2: 400	P2: 1
2016	Pioneer Energy	2-stage	Cu/Zn/Al	Zn-ZSM-5	T1: 175–275	P1: 20	65	6	2	33	59	(54)
		H2/CO = 1			T2: 450	P2: 1
2018	Dow	H2/CO = 3	Cu/Zn/Al	H-SAPO-34	330	20	61	4	<3	93	0	(55)
2018	Dow	H2/CO = 3	Cu/Zn/Al	H-SAPO-34	340	20	69	2	0	98	0	(55)
2018	Dow	H2/CO = 3	Cu/Zn/Al	H-SAPO-34	350	20	66	2	0	97	0	(55)
2018	Dow	H2/CO = 3	Cu/Zn/Al	H-SAPO-34	360	20	65	2	0	97	0	(55)
2018	Dow	H2/CO = 3	Cu/Zn/Al	H-SAPO-34	370	20	59	2	0	97	0	(55)
2018	Dow	H2/CO = 3	Cu/Zn/Al	H-SAPO-34	380	20	51	2	0	97	0	(55)
2018	Dow	H2/CO = 3	Cu/Zn/Al	H-SAPO-34	400	20	40	6	0	94	0	(55)
2018	Dow	H2/CO = 3	Cu/Zn/Al	H-SAPO-34	410	20	34	8	0	91	0	(55)
2018	Dow	H2/CO = 3	Cu/Zn/Al	H-SAPO-34	430	20	19	22	0	77	0	(55)
2018	Dow	H2/CO = 3	Cu/Zn/Al	H-SAPO-34	380	5	3	34	<2	64	0	(55)
2018	Dow	H2/CO = 3	Cu/Zn/Al	H-SAPO-34	380	35	74	4	0	96	0	(55)
2018	Dow	H2/CO = 3	Cu/Zn/Al	H-SAPO-34	380	50	81	5	<1	94	0	(55)
2018	Dow	H2/CO = 2	Cu/Zn/Al	H-SAPO-34	380	50	82	4	0	96	0	(55)
2018	Dow	H2/CO = 4	Cu/Zn/Al	H-SAPO-34	380	50	80	6	0	94	0	(55)
2018	Dow	H2/CO = 5	Cu/Zn/Al	H-SAPO-34	380	50	80	7	<1	92	0	(55)
2018	Dow	H2/CO = 6	Cu/Zn/Al	H-SAPO-34	380	50	79	8	<1	92	0	(55)
2018	Dow	H2/CO = 3	Cu/Zn/Al	H-SAPO-34	380	40	72	5	0	94	0	(55)
2018	Dow	H2/CO/CO2 = 67/23/10	Cu/Zn/Al	H-SAPO-34	380	40	58	3	<1	96	0	(55)
2018	Dow	H2/CO/CO2 = 60/20/20	Cu/Zn/Al	H-SAPO-34	380	40	46	3	<1	96	0	(55)
2018	Dow	H2/CO2 = 3	Cu/Zn/Al	H-SAPO-34	400	40	2b	23	0	70	0	(55)
2018	Dow	H2/CO2 = 3	Cu/Zn/Al	H-SAPO-34	375	40	5b	6	0	85	4	(55)
2018	Dow	H2/CO2 = 3	Cu/Zn/Al	H-SAPO-34	350	40	8b	5	0	83	6	(55)
2018	Dow	H2/CO2 = 3	Cu/Zn/Al	H-SAPO-34	325	40	4b	6	0	34	0	(55)
2018	Dow	H2/CO2 = 3	Cu/Zn/Al	H-SAPO-34	300	40	3b	0	0	1	0	(55)
2018	Dow	H2/CO2 = 3	Cu/Zn/Al	H-SAPO-34	350	28	2b	7	0	69	0	(55)
2018	Dow	H2/CO2 = 3	Cu/Zn/Al	H-SAPO-34	350	2	0b	4	0	84	4	(55)
2018	Dow	H2/CO2 = 1	Cu/Zn/Al	H-SAPO-34	350	40	2b	8	0	84	5	(55)
2018	Dow	H2/CO2 = 10	Cu/Zn/Al	H-SAPO-34	350	40	25b	7	0	91	5	(55)
2018	Dow	H2/CO = 3	Cr/Zn	H-SAPO-34	400	50	67	13	3	82	2	(55)
2018	Dow	H2/CO = 3	Cr/Zn	H-SAPO-34	400	70	82	14	1	83	2	(55)
2018	Dow	H2/CO = 3	Cu/Zn/Al	H-SAPO-5/H-SAPO-34	380	50	79	4	0	83	4	(55)
2018	Dow	H2/CO = 3	Cu/Zn/Al	H-SAPO-18	400	50	69	9	0	89	2	(55)
2018	Dow	H2/CO = 3	Cu/Zn/Al	β-zeolite	385	50	71	13	0	86	2	(55)
2019	Dow	H2/CO = 2	Cr/Zn	H-SAPO-34	400	20	43	8	51c	36c	<5	(56)
2019	Dow	H2/CO = 1.5	Cr/Zn	H-SAPO-34	400	20	35	11	45c	38c	<5	(56)
2019	Dow	H2/CO = 3	Cr/Zn	H-SAPO-34	400	20	50	10	20c	61c	<9	(56)
2019	Dow	H2/CO = 3	Cr/Zn	H-SAPO-34	400	50	76	6	5c	76c	<12	(56)
2019	Dow	H2/CO = 2	Cr/Zn	H-SAPO-34	400	70	38	16	1c	51c	<3	(56)
2019	Dow	H2/CO = 3	Cr/Zn	H-SAPO-34	400	70	80	14	2c	71c	<12	(56)
2019	Dow	H2/CO = 2	Cr/Zn	H-SAPO-34	450	20	32	43	2c	51c	<5	(56)
2020	DICP	H2/CO = 2	Cu/Zn/Al	H-SSZ-13	365	20	9b	2	38	51	10	(57)
2020	DICP	H2/CO = 2	Pd/Zn/Cr	H-SAPO-34	400	25	13b	2	16	80	3	(57)
2020	DICP	H2/CO = 2	Cu/Zn/Al/Cr/Co	H-SAPO-34	370	20	9b	3	67	19	11	(57)
2020	DICP	H2/CO = 2	Cu/Zn	H-ZSM-5	400	25	8b	1	50	41	8	(57)
2020	DICP	H2/CO = 2	Co/Zn/Al	H-SSZ-13	400	25	10b	8	64	13	17	(57)
2020	DICP	H2/CO = 2	Co/Zn/Ti	H-SAPO-34	400	20	5b	3	57	32	8	(57)
2020	DICP	H2/CO = 2	Cu/Zn/Mo	H-SSZ-13	360	8	4b	4	50	42	4	(57)
2020	DICP	H2/CO = 2	Cu/Zn/V	H-SSZ-13	360	8	4b	4	53	31	12	(57)
2020	DICP	H2/CO = 2	Cu/Zn/Mn	H-SSZ-13	360	8	4b	4	63	25	8	(57)
2020	DICP	H2/CO = 2	Pd/Zn/Zr	H-SSZ-13	380	15	4b	4	56	10	30	(57)
2020	DICP	H2/CO = 2	Mo/Zn/Zr/Al	H-SAPO-34	400	30	5b	7	58	26	9	(57)
2020	DICP	H2/CO = 2	Zn/Ti/Ga	H-SAPO-34	400	35	4b	3	57	33	7	(57)
2020	DICP	H2/CO = 2	Co/Zn/Ti/Mn	H-SAPO-34	400	35	7b	5	68	25	2	(57)
2020	DICP	H2/CO = 2	Ca/Mn/Al/Cu/Zn	H-SSZ-13	375	37	16b	3	18	74	5	(57)
2020	DICP	H2/CO = 2	Ca/Mn/Cr/Co	H-MgSAPO-34	415	30	16b	3	16	75	6	(57)
2020	DICP	H2/CO = 2	Fe/Zn/Al/Cr/Na	H-SAPO-34	400	30	9b	6	66	21	7	(57)
2020	DICP	H2/CO = 2	Fe/Zn/Al/Cr/Mg	H-SAPO-34	400	30	10b	3	73	17	8	(57)
2020	DICP	H2/CO = 2	Fe/Zn/Al/Cr/K	H-SAPO-34	400	30	8b	9	76	9	6	(57)
2020	DICP	H2/CO = 2	Fe/Zn/Al/Cr/Ce	H-SAPO-34	400	30	8b	11	67	18	3	(57)
2020	DICP	H2/CO = 2	Fe/Zn/Al/Cr/La	H-SAPO-34	400	30	11b	2	73	13	12	(57)
2020	DICP	H2/CO = 2	Fe/Zn/Ga/Cr/Mn	H-SAPO-34	400	30	18b	3	75	20	2	(57)
2020	DICP	H2/CO = 2	Fe/Zn/Ge/Cr/Mn	H-SAPO-34	400	30	16b	2	70	21	7	(57)
2020	DICP	H2/CO = 2	Fe/Zn/Zr/Cr/Mn	H-SAPO-34	400	30	19b	4	75	17	4	(57)
2020	DICP	H2/CO = 2	Fe/Zn/In/Cr/Mn	H-SAPO-34	400	30	19b	6	66	21	7	(57)
2020	DICP	H2/CO = 2	Fe/Mn/Al/Cr/Na	H-SAPO-34	400	30	9b	6	64	25	6	(57)
2020	DICP	H2/CO = 2	Fe/Mn/Al/Cr/Mg	H-SAPO-34	400	30	10b	3	73	17	8	(57)
2020	DICP	H2/CO = 2	Fe/Mn/Al/Cr/K	H-SAPO-34	400	30	8b	9	74	11	6	(57)
2020	DICP	H2/CO = 2	Fe/Mn/Al/Cr/Ce	H-SAPO-34	400	30	10b	16	60	15	9	(57)
2020	DICP	H2/CO = 2	Fe/Mn/Al/Cr/La	H-SAPO-34	400	30	10b	12	70	16	2	(57)
2021	SXICC	H2/CO = 1.5	Zn/Mn/In/Ga/Ni/Cr/K	H-SAPO-34	420	20	14b	7	84	7	2	(58)
2021	SXICC	H2/CO = 2.5	Zn/Mn/In/Ga/Ni/Cr/K	H-SAPO-34	400	30	23b	7	80	11	2	(58)
2021	SXICC	H2/CO = 2.5	Zn/Mn/In/Ga/Ni/Cr/K	H-SAPO-34	380	50	14b	4	84	11	2	(58)
2021	SXICC	H2/CO = 2.5	Zn/Mn/In/Ga/Ni/Cr/K	H-SAPO-34	390	50	21b	6	80	10	4	(58)
2021	SXICC	H2/CO = 2.5	Zn/Mn/In/Ga/Ni/Cr/K	H-SAPO-34	400	50	18b	9	78	11	2	(58)
2021	SXICC	H2/CO = 2.5	Zn/Mn/In/Ga/Ni/Cr/K	H-SAPO-34	390	60	30b	8	81	9	2	(58)
2021	SXICC	H2/CO = 3.5	Zn/Mn/In/Ga/Ni/Cr/K	H-SAPO-34	400	60	29b	10	71	18	1	(58)
2021	SXICC	H2/CO = 2.5	Zn/Mn/In/Ga/Ni/Cr/K	H-SSZ-13	390	50	19b	4	85	6	4	(58)
2021	SXICC	H2/CO = 1.5	Zn/Mn/In/Ga/Ni/Cr/K	H-ZSM-5	380	80	16b	6	82	9	3	(58)
2021	SXICC	H2/CO = 2.5	Zn/Mn/In/Ga/Ni/Cr/K	H-ZSM-5	410	50	20b	6	76	16	3	(58)
2021	SXICC	H2/CO = 3.5	Zn/Mn/In/Ga/Ni/Cr/K	H-ZSM-5	380	70	26b	8	75	15	2	(58)
2021	TYUT	H2/CO = 2	Zn/Zr	H-SAPO-34/Silicate-1	410	20	9b	12	80	6	2	(59)
2021	DICP	2-stage	Zn/Al	H-SAPO-34	T1: 390	40	28	n.r.	82	n.r.	n.r.	(60)
		H2/CO = 1			T2: 390
2021	DICP	2-stage	Zn/Al/Cr	H-SAPO-18	T1: 390	40	33	n.r.	80	n.r.	n.r.	(60)
		H2/CO = 1			T2: 390
2021	DICP	2-stage	Zn/Al/Zr	H-SSZ-13	T1: 390	40	31	n.r.	78	n.r.	n.r.	(60)
		H2/CO = 1			T2: 390
2021	DICP	2-stage	Cu/Zn/Al	H-SAPO-34	T1: 260	40	58	n.r.	76	n.r.	n.r.	(60)
		H2/CO = 1			T2: 390
2021	DICP	2-stage	Cu/Zn/Al + Al2O3	H-SAPO-34	T1: 260	40	46	n.r.	77	n.r.	n.r.	(60)
		H2/CO = 1			T2: 390
2022	SXICC	H2/CO2 = 3	Ga/Zr	H-SSZ-13	350	30	23b	4	2	94	0	(61)
2022	SXICC	H2/CO2 = 3	Cr	H-SAPO-34	370	5	9b	1	96	2	1	(62)
2022	SXICC	H2/CO2 = 3	Cr/Zn	H-SAPO-34	370	5	5b	5	89	3	2	(62)
2022	SXICC	H2/CO2 = 3	Cr/In	H-SAPO-34	370	5	7b	8	87	3	2	(62)
2022	SXICC	H2/CO2 = 3	Cr/Al	H-SAPO-34	370	5	5b	5	85	3	2	(62)
2022	SXICC	H2/CO2 = 3	Cr/Zr	H-SAPO-34	370	5	5b	7	85	5	3	(62)
2022	Sinopec	H2/CO = 1	Cr	H-ZSM-5	395	20	18	n.r.	n.r.	n.r.	80d	(63)
2022	Sinopec	H2/CO = 1	Mn	H-ZSM-5	395	20	19	n.r.	n.r.	n.r.	82d	(63)
2022	Sinopec	H2/CO = 1	Ce	H-ZSM-5	395	20	16	n.r.	n.r.	n.r.	73d	(63)
2022	Sinopec	H2/CO = 1	Zr	H-ZSM-5	395	20	14	n.r.	n.r.	n.r.	84d	(63)
2022	Sinopec	H2/CO = 1	Zn/Cr	H-ZSM-5	395	20	18	n.r.	n.r.	n.r.	79d	(63)
2022	Sinopec	H2/CO = 1	Zn/Mn	H-ZSM-5	395	20	20	n.r.	n.r.	n.r.	78d	(63)
2022	Sinopec	H2/CO = 1	Zr/In	H-ZSM-5	395	20	15	n.r.	n.r.	n.r.	82d	(63)
2022	Sinopec	H2/CO = 1	Cr/Mn	H-ZSM-5	395	20	18	n.r.	n.r.	n.r.	82d	(63)
2022	Sinopec	H2/CO = 1	Zr/Ce	H-ZSM-5	395	20	15	n.r.	n.r.	n.r.	81d	(63)
2022	Sinopec	H2/CO = 1	Mn	H-ZSM-11	395	20	20	n.r.	n.r.	n.r.	81d	(63)
2022	Sinopec	H2/CO = 1	Mn	H-ZSM-5/Silicalite-1	395	20	17	n.r.	n.r.	n.r.	84d	(63)
2022	Sinopec	H2/CO = 1	Mn	H-ZSM-5/Silicalite-2	395	20	17	n.r.	n.r.	n.r.	83d	(63)
2022	Sinopec	H2/CO = 1	Mn	H-ZSM-11/Silicalite-2	395	20	17	n.r.	n.r.	n.r.	83d	(63)
2022	Sinopec	H2/CO = 1	Mn	H-ZSM-11/Silicalite-1	395	20	18	n.r.	n.r.	n.r.	83d	(63)
2022	Sinopec	H2/CO = 1	Mn	H-ZSM-5	350	80	33	n.r.	n.r.	n.r.	72d	(63)
2022	Sinopec	H2/CO = 0.5	Mn	H-ZSM-5	395	80	28	n.r.	n.r.	n.r.	73d	(63)
2022	Sinopec	H2/CO = 4	Mn	H-ZSM-5	350	50	25	n.r.	n.r.	n.r.	68d	(63)
2022	Sinopec	H2/CO = 1	Mn	H-ZSM-5	395	50	20	n.r.	n.r.	n.r.	77d	(63)
2022	Sinopec	H2/CO = 1	Mn	H-ZSM-5	450	50	23	n.r.	n.r.	n.r.	72d	(63)
2022	Sinopec	H2/CO = 0.5	Mn	H-ZSM-5	395	40	20	n.r.	n.r.	n.r.	79d	(63)
2022	DICP	H2/CO = 2	Zn	H-SAPO-34/18	410	35	24	5	86	5	4	(64)
2022	DICP	H2/CO = 5.5	Zn	H-SAPO-34/18	400	9	38	5	85	8	2	(64)
2022	DICP	H2/CO = 3	Zn	H-SAPO-34/18	380	45	24	3	85	7	5	(64)
2022	DICP	H2/CO = 6	Mn	H-SAPO-34/18	370	100	33	7	71	14	8	(64)
2022	DICP	H2/CO = 3.5	Ce	AlPO-34/18	470	15	28	4	77	11	8	(64)
2022	DICP	H2/CO = 4.5	Bi	H-SAPO-34/18	400	70	56	3	83	9	5	(64)
2022	DICP	H2/CO = 6.5	In	H-SAPO-34/18	380	25	37	7	76	8	9	(64)
2022	DICP	H2/CO = 8.5	Ga	AlPO-34/18	370	5	31	7	69	11	13	(64)
2022	DICP	H2/CO = 1	Zn/Cr	H-SSZ-13/39	370	35	28	5	74	7	14	(64)
2022	DICP	H2/CO = 2.5	Zn/Al	H-SAPO-34/18	410	50	37	2	88	5	5	(64)
2022	DICP	H2/CO = 2.5	Zn/Ga	H-GaAPO-34/18	430	30	58	5	82	6	7	(64)
2022	DICP	H2/CO = 1	Zn/In	H-GaSAPO-34/18	520	40	19	6	87	6	1	(64)
2022	DICP	H2/CO = 0.5	Mn/Cr	H-ZnAPO-34/18	480	90	14	7	68	12	13	(64)
2022	DICP	H2/CO = 3	Mn/Al	H-MgAPO-34/18	470	60	38	3	86	6	5	(64)
2022	DICP	H2/CO = 1.5	Mn/Zr	H-GaAPO-34/18	450	50	37	2	86	6	6	(64)
2022	DICP	H2/CO = 2.5	Mn/In	H-SAPO-34/18	450	50	34	3	88	6	3	(64)
2022	DICP	H2/CO = 3.5	Co/Al	H-SAPO-34/18	350	50	27	3	76	10	11	(64)
2022	DICP	H2/CO = 6	Fe/Al	H-SAPO-34/18	350	70	20	5	85	7	3	(64)
2022	DICP	H2/CO = 4	In/Al/Mn	H-SAPO-34/18	400	60	58	5	80	6	9	(64)
2022	DICP	H2/CO = 4	In/Ga/Mn	AlPO-34/18	400	40	33	7	73	7	13	(64)

^aAbbreviations: n.r. Not reported.

^b% Conversion to hydrocarbons, i.e., exclude (R)WGS activity.

^cC₂–C₃ selectivity.

^dAromatics selectivity.